CN106536686A

CN106536686A - High molecular weight imide containing quaternary ammonium salts

Info

Publication number: CN106536686A
Application number: CN201580038822.1A
Authority: CN
Inventors: H·格林菲尔德; D·J·莫尔顿; P·R·斯蒂文森; D·C·阿特尔斯; J·H·布什
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 2014-05-30
Filing date: 2015-05-29
Publication date: 2017-03-22
Also published as: EP3149127A1; BR112016027993A2; SG11201609725XA; US20170107438A1; WO2015184247A1

Abstract

The present technology is related to imide containing quaternary ammonium salts having a hydrocarbyl substituent of number average molecular weight of 1300 to 3000, and the use of such quaternary ammonium salts in fuel compositions or lubricating compositions to improve the water shedding performance of the fuel or lubricant composition.

Description

HMW quaternary ammonium salt containing acid imide

Invention field

This technology is related to the quaternary ammonium salt containing acid imide for number-average molecular weight being for about the hydrocarbyl substituent of 1300 to about 3000, With drainage (water shedding) performance that this kind of quaternary ammonium salt improves fuel composition in fuel and lubricant composition Purposes.The invention further relates to lubricant compositions lubricating internal combustion engines are used for the following method of at least one：It is wear-resistant, rub Wiping, detergency, dispersion force and/or corrosion control performance.

Background of invention

It is very problematic that deposit in diesel fuel injectors nozzle is formed, and produces incomplete diesel combustion, And therefore power loss and misfire.Traditionally, suppress injector incrustation using polyisobutenyl succinimide detersive, but These materials show effect of going on business in Modern Engine.New class compound based on quaternized polyisobutenyl succinimide Show improved detergency performance is provided in tradition and modern diesel engine.

Although sediment monitoring is the major function of peace and quiet agent molecule requirement, there are a large amount of other performance attributes wanted. One of these is detersive drainage or the ability by oil-in-water emulsion re-dissolved.For example in crude oil or downstream fuel pipeline And the entrainment of water may result in crude oil or stable emulsion and suspended material in fuel during product transfer.This kind of emulsion Filter may be blocked or make the fuel comprising this kind of emulsion unacceptable.This can also produce the etching problem in downstream.

To help drainage process, can be referred to as in the molecule addition fuel or feedstock oil preparaton of demulsifying agent, nothing In being pipeline, at pump or as after market additive.Although demulsifying agent can help drainage process, it is generally desirable to carry New peace and quiet agent molecule for providing improved demulsibility energy.

Summary of the invention

It was found that by with number-average molecular weight (M_n) alkyl of hydrocarbyl substituent more than 1200 replaces acylating agent, for example, gather different Quaternary ammonium salt prepared by butyl amber acid or anhydride produces to provide when being mixed in diesel fuel 1000M_nHydrocarbyl substituent alkyl replace quaternary ammonium salt prepared by acylating agent compare improved demulsibility can quaternary ammonium salt.

Therefore, in an aspect, the present invention is provided comprising with the M more than 1200_nThe (" acyl of quaternary ammonium salt containing acid imide Imines quaternary ammonium salt ") composition.Acid imide quaternary ammonium salt itself can be the product of following components：A () can quaternized chemical combination Thing and (b) be suitable to by nitrogen-containing compound can quaternized amino change into the quaternizing agent of quaternary nitrogen.

Can quaternized compound can be following components product：I () alkyl replaces acylating agent, and (ii) is with energy It is enough replace with alkyl acylation reaction form imido nitrogen-atoms and further have at least one can quaternized amino contain Nitrogen compound.Hydrocarbyl substituent can have more than 1200, the number-average molecular weight of such as 1300-3000.

In one embodiment, can quaternized amino can be primary, secondary or tertiary amino.In another embodiment, hydrocarbon It can be polyisobutenyl succinic anhydride or polyisobutenyl succinic acid that base replaces acylating agent.

In some embodiments, prepare (a) can the reaction of quaternized compound can be more than 80 or 90 or 100 DEG C At a temperature of carry out.In some embodiments, reaction water can be removed.

In other embodiments, quaternizing agent may not include gaultherolin.In identical or different embodiment, Nitrogen-containing compound may not include dimethylamino propylamine.

In other embodiments again, quaternizing agent can for dialkyl sulfate, alkyl halide, alkyl replace carbonic ester, Hydrocarbyl epoxides, carboxylate, Arrcostab or its mixture.In some cases, quaternizing agent can be hydrocarbyl epoxides. In some cases, quaternizing agent can be the hydrocarbyl epoxides combined with acid.In some cases, quaternizing agent can be Oxalate or terephthalate.In one embodiment, oxalate may include dimethyl oxalate.

In some embodiments, above-mentioned acid imide quaternary ammonium salt can further include at least one other additives.One In the case of a little, at least one other additives can for detersive, demulsifying agent, lubricant, cold flow improver, antioxidant or Its mixture.In some cases, at least one other additives can be at least one on-quaternised Hydrocarbyl-substituted succinic acid. In some cases, at least one other additives can replace quaternary ammonium salt at least one alkyl.Wherein it is at least one its Its additive is that hydrocarbyl substituent can be with 100- under the certain situation of on-quaternised or the acid of quaternized Hydrocarbyl-substituted succinic The polyisobutene of 5000 molecular weight.In one embodiment, at least one other additives can be at least one Manny Uncommon compound.

The another aspect of this technology includes with acid imide quaternary ammonium salt as described herein and further has The composition of the fuel of liquid.In some embodiments, fuel can be diesel fuel.

The another aspect of this technology includes with acid imide quaternary ammonium salt as described herein and further viscous with lubrication The composition of the oil of degree.

The method that the another aspect of this technology provides operation internal combustion engine.In one embodiment, method may include step： A () feeds fuel composition in engine, and (b) operates the engine.Fuel composition used in said method can Comprising：(i) fuel at room temperature for liquid, and the composition of (ii) comprising acid imide quaternary ammonium salt as described herein.Another In embodiment, the method for internal combustion engine is operated to may include step：A lubricant oil composite is fed in the crankcase of engine by (), (b) operate the engine.Lubricant oil composite can include the oil of (i) with lubricant viscosity, and (ii) is as described herein contains Acid imide quaternary ammonium salt.

The embodiment of this technology can provide acid imide quaternary ammonium salt and improve (particularly to strengthen combustion in abrasion resistance, friction Material economy), detersive performance (particularly sediment monitoring or varnish control), dispersion force (particularly smoke control or sludge Control) or corrosion control at least one in purposes.

The method that the another embodiment of this technology provides the drainage or demulsibility energy for improving fuel composition.The method Including the composition comprising acid imide quaternary ammonium salt as described herein used in fuel at room temperature for liquid.Also provide comprising such as The composition of acid imide quaternary ammonium salt described herein at room temperature for liquid fuel in improved drainage or demulsibility energy are provided Purposes.

Therefore, disclose (" the acid imide quaternary ammonium of the quaternary ammonium salt containing acid imide comprising the number-average molecular weight with 1300-3000 Salt ") composition.Acid imide quaternary ammonium salt can include the product of following components：Can quaternized compound and be suitable to will be nitrogenous Compound can quaternized amino change into the quaternizing agent of quaternary nitrogen.Can quaternized compound can be following components reaction produce Thing：Wherein there is hydrocarbyl substituent the alkyl of the number-average molecular weight of 1300-3000 to replace acylating agent, and have and can take with alkyl For acylation reaction formed imido nitrogen-atoms and further with least one can quaternized amino nitrogen-containing compound.Can Quaternized amino can be primary, secondary or tertiary amino.

In one embodiment, it can be polyisobutenyl succinic anhydride or polyisobutenyl amber that alkyl replaces acylating agent Amber acid.In yet another embodiment, alkyl replaces the reaction of acylating agent and nitrogen-containing compound enter at a temperature of more than 80 DEG C OK.

In one embodiment, nitrogen-containing compound does not include the compound comprising dimethylamino propylamine.

In another embodiment, quaternizing agent replaces carbonic acid comprising at least one dialkyl sulfate, alkyl halide, alkyl Ester, hydrocarbyl epoxides, carboxylate, Arrcostab or its mixture.In another embodiment, quaternizing agent can be alkyl ring Oxide.Alternatively, quaternizing agent can be the hydrocarbyl epoxides combined with acid.In another embodiment, it is quaternized Agent is oxalate or terephthalate.In yet another embodiment, quaternizing agent does not include gaultherolin.

Described group of quaternary ammonium salt containing acid imide comprising the number-average molecular weight with 1300-3000 (" acid imide quaternary ammonium salt ") Compound can further include at least one other additives.Suitable additive includes but is not limited to detersive, dispersant, anti-breast Agent, lubricant, cold flow improver, antioxidant or its mixture.

In one embodiment, at least one other additive bags are containing at least one Hydrocarbyl-substituted succinic acid or at least A kind of alkyl replaces quaternary ammonium salt.Hydrocarbyl substituent can be the polyisobutene of the molecular weight with 100-5000.

In another embodiment, at least one other additive bags are containing at least one detersive/dispersant, described peace and quiet Agent/dispersant is the hydrophobicity alkyl with least one number-average molecular weight with 100-10000 and at least one polarity knot The amphiphilic species of structure part, the polar moieties are selected from (i) mono amino or polyamino with most 6 nitrogen-atoms, At least one nitrogen-atoms has alkaline performance；(ii) there is the mono amino or polyamino group of alkaline performance with least one nitrogen-atoms The hydroxyl of conjunction；V () is had the mono amino or polyamino of alkaline performance or by carbamate by hydroxyl, at least one nitrogen-atoms Polyoxy-the C of group end capping₂-C₄Alkylene moiety；(vii) derived from succinyl oxide and have hydroxyl and/or amino and/or The structure division of acylamino- and/or acylimino；And/or (viii) is by fortified phenol and aldehyde and the Mannich of monoamine or polyamines The structure division that reaction is obtained.In yet another embodiment, at least one other additives can be comprising at least one Mannich Compound.

In another embodiment, the composition can further include fuel at room temperature for liquid.Fuel can be with For gasoline or diesel oil.Fuel composition can include following at least one：Low number-average molecular weight soap, low number-average molecular weight polyisobutene Succinimide (PIBSI) or its mixture.Low-molecular-weight soap can have the number-average molecular weight (M less than 340_n)。

In yet another embodiment, fuel composition can include 0.01-25ppm metals and 1-12ppm corrosion inhibitors.It is rotten Corrosion inhibitor can be alkenyl succinic acid, and which includes following at least one：Dodecenyl succinic acid (DDSA), hexadecene base Butanedioic acid (HDSA) or its mixture.

In yet another embodiment, fuel composition is comprising with low number-average molecular weight M less than 400_nPIBSI.

The method for also disclosing the water filtering performance for improving gasoline or diesel fuel composition.The method may include to use and include The composition of acid imide quaternary ammonium salt as described above.Acid imide quaternary ammonium salt can be with the gross weight 5-1000 weight based on fuel composition During the amount of amount ppm adds fuel.

In another method, the composition comprising acid imide quaternary ammonium salt can further include the oil with lubricant viscosity.

The method for also disclosing operation internal combustion engine.The method is may include at room temperature for liquid and with wherein comprising acyl During the fuel of the composition of imines quaternary ammonium salt feeds engine and operate engine.Acid imide quaternary ammonium salt can be with based on fuel stack During the amount of gross weight 5-1000 weight ppm of compound adds fuel.

In yet another embodiment, the method for internal combustion engine is operated to may include with the wherein group comprising acid imide quaternary ammonium salt Compound with lubricant viscosity oil feed engine crankcase in and operate engine.Acid imide quaternary ammonium salt can be with based on work Property material 1-5 weight % add oil.Oil with lubricant viscosity can have grey and/or little less than total sulfate of 1 weight % In the phosphorus content of 0.11 weight %.

Also disclose the method for reducing and/or preventing injector deposits.The method is may include with wherein comprising acyl During the fuel composition of the composition of imines quaternary ammonium salt feeds the fuel injector of engine and operate engine.Deposit can be with For internal diesel injector deposit (IDID).In yet another embodiment, deposit can include low number-average molecular weight soap, low number Average molecular weight polyisobutenyl succinimide (PIBSI) or its mixture.

In another embodiment, fuel can be included with the number-average molecular weight (M less than 340_n) molecular weight soap.

In another embodiment, fuel can include 0.01-25ppm metals and 1-12ppm corrosion inhibitors.In another reality Apply in scheme, corrosion inhibitor can be alkenyl succinic acid, and which includes following at least one：Dodecenyl succinic acid (DDSA), hexadecenyl succinic acid (HDSA) or its mixture.

In another embodiment, fuel is comprising with low number-average molecular weight M less than 400_nPIBSI.Fuel can be with For gasoline or diesel oil.In yet another embodiment, engine can include high pressure common rail injectors system.

Also disclosing the composition comprising acid imide quaternary ammonium salt reduces and/or prevents with sending out that gasoline or diesel fuel are operated The purposes of the inside deposit in motivation.In one embodiment, engine can include high pressure common rail injectors system.Again In one embodiment, acid imide quaternary ammonium salt can be used to reduce and/or prevent internal diesel injector deposit (IDID).

Brief description

Fig. 1 shows the demulsification test result of an embodiment of the technology.

Fig. 2 shows the CEC F-23-01XUD-9 result of the tests of an embodiment of the technology.

Fig. 3 shows the CEC F-98-09DW10B result of the tests of an embodiment of the technology.

Detailed description of the invention

Each feature and embodiment are described below by non-limiting elaboration.

The one side of this technology is related to comprising the number-average molecular weight (" M with 1300-3000_n") quaternary ammonium containing acid imide The composition of salt (" acid imide quaternary ammonium salt ").

The number-average molecular weight of material described herein is used using gas permeation chromatography (GPC) and is equipped with RI-detector With Waters Empower^TMThe Waters GPC 2000 of data capture and analysis software are measured.Post be polystyrene (PLgel, 5 μm, can be obtained by Agilent/Polymer Laboratories, Inc.).For mobile phase, they are being injected in GPC holes In the past each sample was dissolved in tetrahydrofuran and was filtered with PTFE filters.

2000 operating conditions of Waters GPC：

Syringe, post and pump/solvent room temperature：40℃

Autosampler is controlled：Run time：40 minutes

Volume injected：300μl

Pump：System pressure：～90 bar (maximum pressure limitations：270 bars, the minimum pressure limit：0psi)

Flow velocity：1.0ml/ minute

Differential refractometer (RI)：Sensitivity：-16；Scale factor：6

M with 1300-3000 _n Quaternary ammonium salt containing acid imide (" acid imide quaternary ammonium salt ")

The preparation of quaternary ammonium salt generally produces the mixture of the compound comprising one or more quaternary ammonium salt, and the mixture can Can be difficult to dividually define with the processing step for preparing quaternary ammonium salt.In addition, the method for producing quaternary ammonium salt may give most It is influential in terms of the unique structural characteristics of whole quaternary ammonium salt product, this may affect the performance of quaternary ammonium salt product.Therefore, one In individual embodiment, the acid imide quaternary ammonium salt of this technology can be described as the product of following components：A () can quaternized chemical combination Thing, and (b) quaternizing agent.As used herein, referring to including equal with regard to the number with 1300-3000 with regard to acid imide quaternary ammonium salt Referring to for the compound mixture of molecular weight, including one or more quaternary ammonium salt as described herein, and refers to quaternary ammonium salt sheet Body.

For prepare acid imide quaternary ammonium salt (a) of itself can quaternized compound can be that the reaction of following components is produced Thing：I () alkyl replaces acylating agent, and (ii) nitrogen-containing compound.More particularly, (a) the alkyl replacement acylating agent of (i) can be by apparatus It is made up of the acylating agent of the hydrocarbyl substituent functionalization of the number-average molecular weight of 1300-3000.

Example of quaternary ammonium salt and preparation method thereof is described in following patent：US 4,253,980、US 3,778,371、US 4,171,959, US 4,326,973, US 4,338,206, US 5,254,138 and US 7,951,211, by quote tied Close herein.

With regard to can quaternized compound, specifically, alkyl replaces acylating agent and nitrogen-containing compound, and quaternizing agent Details is provided below.

Alkyl replaces acylating agent

For prepare can the alkyl of quaternized compound to replace acylating agent can be long chain hydrocarbons, usual polyolefinic alkyl Replace based precursor with single unsaturated carboxylic acid reactant, such as (i) α, β-mono- unsaturation C₄-C₁₀Dicarboxylic acids for example fumaric acid, itaconic acid, Maleic acid；(ii) acid anhydride or C of derivative (i) such as (i)₁-C₅The product of the derivative monoesters of alcohol or diester.

Hydrocarbyl substituent is long chain hydrocarbon groups.In one embodiment, alkyl can have the number-average molecular weight of 1300-3000 (M_n).The M of hydrocarbyl substituent_nCan also be 1500-2800 or 2900, or 1700-2700, or 1900-2600, or 2000-2500.In one embodiment, hydrocarbyl substituent can be any chemical combination containing alkene key shown in below general formula Thing：

(R¹)(R²) C=C (R⁶)(CH(R⁷)(R⁸)) (I)

Wherein R¹And R²It is each independently hydrogen or hydrocarbyl group.R⁶、R⁷And R⁸It is each independently hydrogen or hydrocarbyl group；It is excellent At least one is selected to be the hydrocarbyl group comprising at least 20 carbon atoms.

Olefin polymer for reacting with single unsaturated carboxylic acid may include the C comprising main mole₂-C₂₀, such as C₂- C₅The polymer of monoolefine.This kind of alkene includes ethene, propylene, butylene, isobutene, amylene, 1- octenes or styrene.Polymer Can be homopolymers such as polyisobutene, and the copolymer of two or more in this kind of alkene, such as ethene and propylene；Fourth Alkene and isobutene；The copolymer of propylene and isobutene.Other copolymers include the polymer monomers of wherein minority molar amount, for example 1-10 mole of % is C₄-C₁₈The copolymer of those of alkadienes, such as isobutene and butadiene；Or ethene, propylene and 1,4- oneself The copolymer of diene.

In one embodiment, at least one R of formula (I) is derived from polybutene, i.e. C₄Alkene, including 1- butylene, 2- The polymer of butylene and isobutene.C₄Polymer may include polyisobutene.In another embodiment, at least one R of formula (I) Derived from ethylene-alpha-olefin polymers, including Ethylene-Propylene-Diene polymer.Ethylene-alpha-olefin copolymer and ethene-rudimentary alkene Hydrocarbon-diene terpolymer is described in a large amount of patent documents, special including European Patent Publication EP0279863 and the following U.S. Profit：3,598,738；4,026,809；4,032,700；4,137,185；4,156,061；4,320,019；4,357,250；4, 658,078；4,668,834；4,937,299；In 5,324,800, will be the correlation of its these polyvinyl public by quoting Open content to be incorporated herein in.

In another embodiment, the alkene key of formula (I) is mainly the ethenylidene that following formula is represented：

Wherein R is alkyl,

Wherein R is alkyl.

In one embodiment, the vinylidene content of formula (I) can comprising at least 30 moles % ethenylidenes, at least 50 Mole % ethenylidenes, or at least 70 moles % ethenylidenes.This kind of material and preparation method thereof is described in United States Patent (USP) Nos.5,071,919；5,137,978；5,137,980；5,286,823、5,408,018、6,562,913、6,683,138、7, 037,999 and U.S. Publication Nos.20040176552A1,20050137363 and 20060079652A1 in, by quote will Which is expressly incorporated into herein.This kind of product is with trade nameBy BASF and with trade name TPC 1105^TMWith TPC 595^TMIt is commercial by Texas PetroChemical LP.

In other embodiments, it can be " routine " vinylidene polyisobutylenes (PIB) that alkyl replaces acylating agent, wherein It is ethenylidene head group by head group of nuclear magnetic resonance (NMR) measurement less than 20%.Alternatively, alkyl replaces acylating agent Can be medium-ethenylidene PIB or high-ethenylidene PIB.In medium-ethenylidene PIB, it is the head base of ethenylidene The percentage of group can be more than 20% to 70%.In height-ethenylidene PIB, it is the head group of ethenylidene head group Percentage is more than 70%.

It is this that alkyl is prepared by the reaction of single unsaturated carboxylic acid reactant and formula (I) compound to replace the method for acylating agent In field known to and be disclosed in following patent：United States Patent (USP) Nos.3,361,673 and 3,401,118, to cause to carry out heat " alkene " reacts；United States Patent (USP) Nos.3,087,436；3,172,892；3,272,746、3,215,707；3,231,587；3,912, 764；4,110,349；4,234,435；6,077,909；6,165,235, and it is incorporated herein by reference.

Preparing alkyl replaces other methods of acylating agent find in below with reference to document：United States Patent (USP) Nos.5,912, 213；5,851,966；With 5,885,944, it is incorporated into herein by quoting.

Nitrogen-containing compound

The present composition is comprising with the nitrogen-atoms of acylation reaction and further can have can quaternized amino Nitrogen-containing compound.Can quaternized amino be nitrogen-containing compound on can be used for quaternizing agent react to become any of quaternary ammonium Primary, secondary or tertiary amino.

In one embodiment, nitrogen-containing compound can be expressed from the next：

Wherein X is the alkylidene containing 1-4 carbon atom；R³And R⁴For alkyl.

Dimethylamino propylamine, N, N- bis- can be may include but be not limited to the example of the nitrogen-containing compound of acylation reaction Methyl-amino propylamine, N, N- diethyl-amino propylamine, N, N- dimethyl-amino ethamine, ethylenediamine, 1,2- propane diamine, 1,3- Propane diamine, isomers amine, including butanediamine, pentanediamine, hexamethylene diamine and heptamethylene diamine, diethylenetriamines, dipropylenetriamine, two Butylidene triamine, trien, tetren, penten, hexa and double (hexa-methylenes) Triamine, diaminobenzene, diamino-pyridine, N- methyl -3- amino -1- propylamine or its mixture.With acylation reaction and can enter One step have can quaternized amino nitrogen-containing compound can further include aminoalkyl replace heterocyclic compound, such as 1- (3- aminopropyls) imidazoles and 4- (3- aminopropyls) morpholine, 1- (2- amino-ethyls) piperidines, 3,3- diamino-Ns-methyl dipropyl Amine, 3,3'- imino groups are double (N, N- dimethyl propylamine).In some embodiments, nitrogen-containing compound does not include dimethylamino Propylamine.

In one embodiment, nitrogen-containing compound can be imidazoles, for example, be shown below：

Wherein R is can to replace acylating agent condensation and the amine with 3-8 carbon atom with the alkyl.

In one embodiment, nitrogen-containing compound can be represented by Formula X：

Wherein each X can be individually C₁-C₆Alkylene, and each R can be individually hydrogen or C₁-C₆Alkyl.In a reality Apply in scheme, X can be such as C₁、C₂Or C₃Alkylidene.In identical or different embodiment, each R can be such as H Or C₁、C₂Or C₃Alkyl.

Can quaternized compound

Above-mentioned alkyl replaces acylating agent and nitrogen-containing compound one can react that to be formed can quaternized compound.Alkyl replaces acyl The method and technique of agent and nitrogen-containing compound reaction is well known in the art.

In embodiments, alkyl replace reaction between acylating agent and nitrogen-containing compound can more than 80 DEG C, or 90 DEG C, or in some cases, 100 DEG C, such as 100 to 150 or 200 DEG C, or carry out at a temperature of 125-175 DEG C.Upper At a temperature of stating, water can be produced during condensation, which is referred to herein as reaction water.In some embodiments, can be by reaction water Remove during reaction so that reaction water does not return in reacting single step reaction of going forward side by side.

Alkyl replacement acylating agent and nitrogen-containing compound can be with 1:1 ratio reaction, but reaction can also include 3:1-1:1.2, Or 2.5:1-1:1.1, in some embodiments, 2:1-1:(i.e. alkyl replaces acylating agent to 1.05 each reactant:Nitrogen Compound).

Quaternizing agent

When can quaternized compound, i.e. above-mentioned alkyl replace the product and quaternizing agent of acylating agent and nitrogen-containing compound During reaction, quaternary ammonium salt can be formed.Suitable quaternizing agent may include that for example dialkyl sulfate, alkyl halide, alkyl replace carbonic acid Ester；Hydrocarbyl epoxides, carboxylate, Arrcostab and its mixture.

In one embodiment, quaternizing agent may include alkyl halide, such as chloride, iodide or bromide； Alkylsulfonate；Dialkyl sulfate such as dimethyl suflfate and dithyl sulfate；Sultone；Alkylphosphonate, such as phosphoric acid C_1-12Trialkyl ester；Di(2-ethylhexyl)phosphate C_1-12Arrcostab；Borate, boric acid C_1-12Arrcostab；Alkyl nitride；Alkyl nitrate；Carbon Acid dialkyl ester, such as dimethyl oxalate；Chain acid alkyl ester, such as gaultherolin；Bis--C of O, O-_1-12Two thio phosphorus of alkyl Hydrochlorate；Or its mixture.

In one embodiment, quaternizing agent can be derived from dialkyl sulfate, such as dimethyl suflfate or sulfuric acid two Ethyl ester, N- oxides, such as sultone, propane and butane sultone；Alkyl, acyl group or aryl halide, such as methyl and second Base chloride, bromide or iodide, or benzyl chloride, and alkyl (or alkyl) replacement carbonic ester.If alkyl halide is benzyl Chlorine, then aromatic ring is optionally further by alkyl or alkenyl replacement.

Alkyl replaces the alkyl (or alkyl) of carbonic ester include 1-50,1-20,1-10 or 1-5 carbon atom per group. In one embodiment, alkyl replaces carbonic ester to include 2 alkyl, and the alkyl can be identical or different.Suitably Alkyl replaces the example of carbonic ester to include dimethyl carbonate or diethyl carbonate.

In another embodiment, quaternizing agent can be hydrocarbyl epoxides, for example, be shown below：

Wherein R¹、R²、R³And R⁴H or the alkyl comprising 1-50 carbon atom can independently be.The reality of hydrocarbyl epoxides Example includes：Ethylene oxide, propylene oxide, butylene oxide, styrene oxide and combinations thereof.In one embodiment, it is quaternized Agent does not contain any styrene oxide.

In some embodiments, hydrocarbyl epoxides can be alcohol functionalized epoxides, C₄-C₁₄Epoxides and its Mixture.The C of example₄-C₁₄Epoxides for Formula X II those, wherein R¹、R²、R³And R⁴H or C can independently be₄-C₁₄Hydrocarbon Base.In one embodiment, epoxides can be C₄-C₁₄Epoxides.The ring of quaternizing agent is suitable in this technique Oxide may include such as C with linear hydrocarbyl substituents₄-C₁₄Epoxides, such as 2- ethyls oxirane, 2- propyl group Oxirane etc., and the C with branched and ring-type or aromatic substituent₄-C₁₄Epoxides, such as styrene oxide.C₄- C₁₄Epoxides may also include epoxidation triglycerides, fat or oil；Epoxidized fat acid alkyl ester；And its mixture.Again In one embodiment, hydrocarbyl epoxides can be C₄-C₂₀Epoxides.

The alcohol functionalized epoxides of example may include those of Formula X II, wherein R¹、R²、R³And R⁴Can independently be H or Hydroxyl alkyl.In one embodiment, hydroxyl alkyl can include 2-32, or 3-28, or or even 3-24 carbon original Son.The alcohol functionalized epoxide derivate of example may include such as glycidol etc..

In some embodiments, hydrocarbyl epoxides can be applied in combination with acid.It is used together with hydrocarbyl epoxides Acid can be separate component, such as acetic acid.In other embodiments, there may be a small amount of acid constituents, but be<0.2 or very Extremely<0.1 every mole of equimolar acid alkyl acylating agent.These acid also can be with above-mentioned other quaternizing agents, including alkyl replaces carbonic ester Hereinafter described associated materials are used together.

In some embodiments, quaternizing agent is without any substituent containing more than 20 carbon atoms.

In another embodiment, quaternizing agent can be the ester of the carboxylic acid that quaternary ammonium salt can be formed with reactive tertiary amine, or The ester of person's polycarboxylic acids.In general, this kind of material can be described as the compound with following structure：

R¹⁹- C (=O)-O-R²⁰ (XIII)

Wherein R¹⁹For optionally substituted alkyl, thiazolinyl, aryl or alkaryl, and R²⁰It is the hydrocarbon comprising 1-22 carbon atom Base.

Suitable compound includes the ester of the carboxylic acid with 3.5 or less pKa.In some embodiments, compound It is the ester selected from the carboxylic acid for replacing aromatic carboxylic acid, alpha-hydroxy carboxylic acid compounds and polycarboxylic acids.In some embodiments, compound is replacement The ester of aromatic carboxylic acid, therefore, R¹⁹For substituted aryl.R¹⁹Can be the substituted aryl with 6-10 carbon atom, phenyl or naphthalene Base.R¹⁹Following substituent group can be selected from by one or more suitably：Carbon alkoxyl, nitro, cyano group, hydroxyl, SR` or NR`R ``, wherein R` and R`` can each independently be hydrogen, or optionally substituted alkyl, thiazolinyl, aryl or carbon alkoxyl.At some In embodiment, R` and R`` is each independently hydrogen or comprising 1-22,1-16,1-10, or or even 1-4 carbon atom Optionally substituted alkyl.

In some embodiments, the R in above formula¹⁹Be by one or more selected from following substituent group aryl：Hydroxyl Base, carbon alkoxyl, nitro, cyano group and NH²。R¹⁹Can be polysubstituted aryl, such as trihydroxy phenyl, but it is also possible to singly to take For aryl, such as aryl that ortho position replaces.R¹⁹OH, NH can be selected from₂、NO₂Or the substituent group of COOMe.Suitably, R¹⁹For hydroxyl The aryl that base replaces.In some embodiments, R¹⁹For 2- hydroxy phenyls.R²⁰Can be alkyl or alkaryl, such as comprising 1- 16 carbon atoms, or 1-10, or the alkyl or alkaryl of 1-8 carbon atom.R²⁰Can be methyl, ethyl, propyl group, fourth Base, amyl group, benzyl or its isomers.In some embodiments, R²⁰For benzyl or methyl.In some embodiments, quaternary ammonium Agent is gaultherolin.In some embodiments, quaternizing agent does not include gaultherolin.

In some embodiments, ester of the quaternizing agent for alpha-hydroxy carboxylic acid compounds.This kind of compound being suitable in this article is retouched It is set forth in EP 1254889.The example of the suitable compound of the residue comprising alpha-hydroxy carboxylic acid compounds includes (i) 2- hydroxy-iso-butyric acids Methyl-, ethyl-, propyl group-, butyl-, amyl group-, hexyl-, benzyl-, phenyl-and allyl ester；(ii) 2- hydroxy-2-methyls fourth The methyl of acid-, ethyl-, propyl group-, butyl-, amyl group-, hexyl-, benzyl-, phenyl-and allyl ester；(iii) 2- hydroxyls -2- The methyl of ethyl butyric acid-, ethyl-, propyl group-, butyl-, amyl group-, hexyl-, benzyl-, phenyl-and allyl ester；(iv) lactic acid Methyl-, ethyl-, propyl group-, butyl-, amyl group-, hexyl-, benzyl-, phenyl-and allyl ester；(v) first of hydroxyacetic acid Base-, ethyl-, propyl group-, butyl-, amyl group-, hexyl-, pi-allyl-, benzyl-and phenylester.In some embodiments, quaternary ammonium Agent includes 2- hydroxy-methyl isobutyl acids.

In some embodiments, ester of the quaternizing agent comprising polycarboxylic acids.In this definition, we mean that including dicarboxylic acids With the carboxylic acid with more than two acid structure part.In some embodiments, ester is with the alkane comprising 1-4 carbon atom The Arrcostab of base.Suitable example include the diester of oxalic acid, the diester of phthalic acid, the diester of maleic acid, the two of malonic acid The diester or three esters of ester or citric acid.

In some embodiments, quaternizing agent is the ester of the carboxylic acid with the pKa less than 3.5.Compound bag wherein In this kind of compound containing more than one acid groups, the first dissociation constant is we mean that.Quaternizing agent may be selected from the ester of carboxylic acid, institute Carboxylic acid is stated selected from one or more of：Oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoyl Acid, aminobenzoic acid and 2,4,6- trihydroxybenzoic acids.In some embodiments, quaternizing agent includes dimethyl oxalate, right Phthalic acid ester, such as dimethyl terephthalate (DMT), and 2- nitrobenzene methyls.

It is also possible to use can be coupled it is more than one can quaternized compound quaternizing agent." coupling " is more than one can quaternary ammonium Change compound mean at least two can quaternized compound can with identical quaternizing agent reaction be connected by quaternizing agent with being formed At least two can quaternized compound compound.In some cases, this kind of quaternizing agent is alternatively referred to as even herein Connection and may include such as polyepoxide at quaternizing agent, such as two-, three-or higher epoxides；Poly- halide；Epoxy radicals- Halide, aromatic polyester and its mixture.

In one embodiment, quaternizing agent can be polyepoxide.Polyepoxide may include such as bunching water Glyceryl, which may include such as two-epoxy radicals octane；Ethylene glycol diglycidylether；Neopentylglycol diglycidyl ether；1,4- Butanediol diglycidyl ether；3 (double (glycidyl oxy methyl)-methoxyl groups) -1,2- propane diols；1,4- hexamethylene diformazans Alcohol diglycidyl ether；Bicyclic oxygen cyclooctane, bisphenol A diglycidyl ether, 4- vinyl -1- cyclohexene diepoxides； N, N- diglycidyl -4-4 glycidyloxyanilines；1,6- hexane diglycidyl ethers；Trimethylolpropane tris shrink Glycerin ether；Polypropylene glycol diglycidyl ether；Polycyclic oxidation triglycerides, fat or oil；And its mixture.

In one embodiment, quaternizing agent can be derived from polyhalide, such as chloride, iodide or bromide. This kind of polyhalide may include but be not limited to pentamethylene bromide；Bis- iodobutanes of 1,4-；1,5- dichloropentane；1,12- dichloros ten Dioxane；1,12- dibromo-dodecanes；1,2- ethylidene periodides；Glycol dibromide；And its mixture.

In one embodiment, quaternizing agent can be epoxy radicals-halide, such as epichlorohydrin etc..

Quaternizing agent can also be poly- aromatic ester.The example of poly- aromatic ester includes but is not limited to the double (methylbenzenes of 4,4 '-epoxide Formic acid esters)；Dimethyl terephthalate (DMT)；And its mixture.

In certain embodiments, can the mol ratio of quaternized compound and quaternizing agent be 1:0.1-2, or 1:1- 1.5, or 1:1-1.3.In some embodiments, particularly when using be coupled quaternizing agent when, can quaternized compound with The ratio of quaternizing agent can be 2:1-1:1.

Any of the above described quaternizing agent, including hydrocarbyl epoxides can be applied in combination with acid.Suitable acid includes carboxylic acid, for example Acetic acid, propionic acid, 2 ethyl hexanoic acid etc..

In some embodiments, quaternizing agent can be in the presence of proton solvent such as 2-Ethylhexyl Alcohol, water and combinations thereof Use.In some embodiments, quaternizing agent can be used in the presence of acid.In yet another embodiment, quaternizing agent can Use in the presence of acid and proton solvent.In some embodiments, acid can be except being present in the structure of acylating agent Acid constituents beyond acid groups.In other embodiments, reaction can be free of, or be substantially free of different from being present in acylating agent Structure in acid groups any other acid constituents." not containing " means to be entirely free of, and " being substantially free of " means not substantive shadow Ring the amount of the necessary of composition or basic and new features, e.g., less than 1 weight %.

Structure

Although the method for preparing quaternary ammonium salt can be produced except processing step and be not easy the mixture for defining, in certain situation Under, it is contemplated that some structural constituents.

In some embodiments, quaternary ammonium salt can be included, substantially by or the cation composition that is expressed from the next：

Wherein R²¹It is the alkyl comprising 1-10 carbon atom；R²²It is the alkyl comprising 1-10 carbon atom；R²³It is comprising 1- The alkylene of 20 carbon atoms；R²⁴It is or 107 to 200 or 210 carbon atoms comprising 92-215 carbon atom, or 120- 195 carbon atoms, or the alkyl of 135-190 or 140 to 180 or 185 carbon atom；And X is derived from quaternizing agent Group.

Wherein R²³It is the alkylene comprising 1-20 carbon atom；R²⁴It is comprising 92-215 carbon atom or 107 to 200 Or 210 carbon atoms, or 120-195 carbon atom, or the alkyl of 135-190 or 140 to 180 or 185 carbon atom； And X is the group derived from quaternizing agent.

In some embodiments, quaternary ammonium salt can be included, substantially by or the coupling quaternary ammonium compound group that is expressed from the next Into：

Wherein Q and Q ' be it is identical or different, and represent can quaternized compound, m and n independently is the integer of 1-4, and Xc is represented derived from coupling quaternizing agent, such as group of BDDE or bisphenol A diglycidyl ether. Example is coupled any one that quaternary ammonium compound may include in such as following formula：

Integers of the wherein a for 2-8.Wherein a is that the example of 2 or 3 Formula X X can for example respectively by Formula X X ' and XX " represent：

Even other examples be coupled quaternary ammonium compound can be provided in for example following Formula X XIV：

Integers of the wherein a for 2-8.Wherein a is that the example of 2 or 3 Formula X XIV can be respectively for example by Formula X XIV ' and XXIV " Represent：

In all：R²¹-R²⁴With Xc as described above.

Composition

In one embodiment, this technology is provided comprising the composition containing acid imide quaternary ammonium salt, and said composition is in combustion The purposes of the drainability of fuel composition is improved in feed composition.In another embodiment, this technology is provided comprising sub- containing acyl The composition of amine quaternary ammonium salt, and purposes of the said composition in the lubricating composition with the oil with lubricant viscosity.

Fuel

It is liquid and the fuel for fuel is supplied to engine that the present composition is can be included under room temperature.Fuel generally exists It is liquid under environmental condition such as room temperature (20-30 DEG C).Fuel can be hydrocarbon fuel, nonhydrocarbon fuel or its mixture.Hydrocarbon fuel can Think petroleum distillate, including such as the gasoline defined in EN228 or ASTM specifications D4814, or such as EN590 or ASTM specifications The diesel fuel of D975 definition.In one embodiment of the invention, fuel is gasoline, and in other embodiments, fuel is Doped fuel or unleaded gas.In another embodiment of the present invention, fuel is diesel fuel.Hydrocarbon fuel can be by day The hydrocarbon that so prepared by gas artificial oil method, including the hydrocarbon for for example being prepared by method such as fischer tropsch process.Nonhydrocarbon fuel can be oxygen-containing group Compound, commonly referred to oxygenate, including alcohol, ether, ketone, carboxylate, itroparaffin or its mixture.Nonhydrocarbon fuel may include example Such as methyl alcohol, ethanol, methyl tertiary butyl ether(MTBE), MEK, the ester-exchanged oil from plant and animal and/or fat such as rape seed oil methyl esters With soybean oil methyl esters, and nitromethane.The mixture of hydrocarbon and nonhydrocarbon fuel may include such as gasoline and methyl alcohol and/or ethanol, bavin Oil fuel and ethanol, and diesel fuel and ester exchange vegetable oil such as rape seed oil methyl esters.In one embodiment of the invention, liquid Fluid fuel is emulsion of the water in hydrocarbon fuel, nonhydrocarbon fuel or its mixture.In several embodiments of the present invention, fuel can With being 5000ppm or less, 1000ppm or less, 300ppm or less, 200ppm or less, 30ppm or more based on weight It is little, or 10ppm or less sulfur content.In another embodiment, fuel can be with based on the sulphur that weight is 1-100ppm Content.In one embodiment, fuel includes 0ppm to 1000ppm, or 0-500ppm, or 0-100ppm, or 0- 50ppm, or 0-25ppm, or 0-10ppm, or 0-5ppm alkali metal, alkaline-earth metal, transition metal or its mixture. In another embodiment, fuel includes 1-10 weight ppm alkali metal, alkaline-earth metal, transition metal or its mixture.In this area Know comprising alkali metal, alkaline-earth metal, transition metal or its mixture fuel have larger formation deposit and therefore Make the tendency of co-rail ejector incrustation or blocking.Fuel of the present invention is present in fuel stack with the primary amount for being typically larger than 50 weight % In compound, in other embodiments, more than 90 weight %, more than 95 weight %, more than 99.5 weight %, or being more than 99.8 weight % are present.

Handling rate of the present invention containing the imido quaternary ammonium salt of HMW (acid imide quaternary ammonium salt) and fuel is 5- 1000ppm or 5-500ppm, or 10-250ppm, or 10-150ppm, or 15-100ppm.In other embodiments, Handling rate may range from 250-1000ppm, or 250-750ppm, or 500-750ppm or 250ppm to 500ppm.

Oil with lubricant viscosity

In lubricating composition embodiment, the present composition can include the oil with lubricant viscosity.This kind of oil includes Natural and artificial oil, derived from being hydrocracked, hydrogenating and hydrorefined oil, does not refine, refines, refined oil, or its mixing again Thing.Do not refine, refine and refined oil is described in more detail in International Publication WO2008/147704, [0054th]-[0056] section again Middle offer.The more detailed description of natural and artificial oil is provided in [0058th]-[0059] section of WO2008/147704 respectively. Artificial oil also can be prepared by fischer-tropsch reaction, and the typically Fischer-Tropsch hydrocarbon or wax of hydroisomerization.In an embodiment party In case, oil can be prepared by Fischer-Tropsch natural gas synthetic oil synthesis program and other natural gas synthetic oils.

Oil with lubricant viscosity is also selected from such as the American Petroleum Institute (API) Base Any one in I-V group base oils described in Oil Interchangeability Guidelines.5 base oil groups are as follows：I groups： >0.03% sulphur or<90% saturate and viscosity index (VI) 80-120；II groups：<0.03% sulphur and >=90% saturate and viscosity index (VI) 80-120；III groups：<0.03% sulphur and >=90% saturate and viscosity index (VI) >=120；IV groups：All polyalphaolefins；V groups：It is all Other base oils.I, II and III group is commonly referred to mineral oil basestocks.

Gross weight of exemplary process rate of the present invention containing the imido quaternary ammonium salt of HMW and lubricating oil based on lubricating oil Measure as 0.1-10 weight % or 0.5-5 weight % or 0.5-2.5 weight % or 0.5-1 weight % or 0.1-0.5 weights Amount % or 1-2 weight %.The amount of the oil with lubricant viscosity for existing is usually and is deducting of the present inventionization from 100 weight % The later surplus of the amount sum of compound and other performance additive.

Lubricating composition can be concentrate and/or the form for preparing lubricant completely.If lubricating composition of the present invention (include additive described herein) (which can combine with other oil and finally be lubricated with completely or partially being formed for the form of concentrate Agent), then these additives include 1 with the ratio of the oil with lubricant viscosity and/or flux oil:99-99:1 weight meter or 80: 20-10:The scope of 90 weight meters.

It is miscellaneous

Fuel of the present invention and/or lubricant compositions include above-mentioned acid imide quaternary ammonium salt and also can include one or more Other additives.It is used for application therein depending on results needed and composition, this kind of other performance additive can add any In the composition.

Although any other performance additive described herein can be used for any fuel of the present invention and/or lubricant compositions In, other additives are used in particular for fuel and/or lubricant compositions below：Antioxidant, corrosion inhibitor, different from above-mentioned Those detersive and/or dispersant additives, cold flow improver, foam inhibitor, demulsifying agent, lubricant, metal deactivator, valve Seat shrinkage depression additive, biocide, antistatic additive, deicer, fluidizing reagent, combustion improver, sealing sweller, wax control polymerization Thing, antisludging agent, gas hydrate inhibitor or its any combinations.

The demulsifying agent for being suitable to be used together with above-mentioned acid imide quaternary ammonium salt may include but be not limited to aromatic yl sulphonate and gather Alcohol alcoxylates, such as polyethylene glycol oxide and polyoxypropylene copolymer etc..Demulsifying agent can also include nitrogen-containing compound, for exampleOxazoline and imidazolinium compounds, and fatty amine, and mannich compound.Mannich compound is that alkylphenol and aldehyde are (outstanding Which is formaldehyde) and amine (especially amine condensation product and polyalkylene polyamine) product.Material described in following United States Patent (USP) Material is illustrative：United States Patent (USP) Nos.3,036,003；3,236,770；3,414,347；3,448,047；3,461,172；3, 539,633；3,586,629；3,591,598；3,634,515；3,725,480；3,726,882；With 3,980,569, by drawing It is herein with being incorporated into.Other suitable demulsifying agents be for example alkyl substituted phenol-and naphthalene sulfonate alkali metal or Alkali salt, and the alkali metal or alkali salt of aliphatic acid, and neutral compound, such as alcohol alkoxylates, for example Alcohol ethoxylate, such as phenol alcoxylates, tert-butyl phenol ethoxylate and tert-amyl phenol ethoxylate, fat The condensation product of fat acid, alkylphenol, ethylene oxide (EO) and propylene oxide (PO), such as including the shape of Pluronic PE 6800 Formula, polyethyleneimine or polysiloxanes.Any commercially available demulsifying agent can suitably be enough in fuel provide 5-50ppm place The amount of reason rate is used.In one embodiment, there is no demulsifying agent in fuel and/or lubricant compositions.Demulsifying agent Can be used alone or in combination.Some demulsifying agents are for example commercial by Nalco or Baker Hughes.

Suitable antioxidant includes such as hindered phenol or derivatives thereof, and/or diaryl amine or derivatives thereof.Suitably Detersive/dispersant additives include such as polyetheramine or nitrogenous detersive, including but not limited to PIB amine detersive/dispersant, Succinimide detersive/dispersant and other quaternary salt detersive/dispersants, including season derived from polyisobutyl group succinimide Ammonium PIB/ amine and/or acid amides dispersant/detersive.Suitable cold flow improver includes such as maleic anhydride and cinnamic ester Change the copolymer of copolymer and/or ethene and vinyl acetate.Suitable lubricity modifier or friction improver are typically based on Aliphatic acid or fatty acid ester.Typical example is ready denier oil acid, as described in such as WO98/004656, and single oleic Ester.United States Patent (USP) No.6, the product of naturally occurring or synthetic oil, such as triglycerides, and alkanolamine described in 743,266B2 It is also suitable and makees lubricity modifier.Other examples include the business ready denier oil acid comprising polycyclic hydrocarbon and/or rosin acid.Properly Metal deactivator include such as aromatic triazole or derivatives thereof, including but not limited to BTA.Other suitable metals subtract Agent live for such as salicyclic acid derivatives,-two salicylidene -1 of such as N, N ', 2- propane diamine.Suitable valve seat shrinkage depression additive bag Include such as alkali metal sulfosuccinates.Suitable foam inhibitor and/or defoamer include such as organopolysiloxane, such as poly- two Methylsiloxane, PES-4, polydiethylsiloxane, polyacrylate and polymethacrylates, trimethyl-three Fluoro- propylmethylsiloxane etc..Suitable fluidizing reagent includes such as mineral oil and/or poly- (alpha-olefin) and/or polyethers.Burning changes Entering agent includes such as octane and cetane number improver.Suitable cetane number improver is for example aliphatic nitrate, such as 2- Ethylhexyl nitrate and cyclohexyl nitrate, and peroxide, such as di-t-butyl peroxide.

May be present in fuel of the present invention and/or the other performance additive in lubricant compositions is also included by making α-hydroxyl Base acid and amine and/or alcohol, the diester for reacting optionally in the presence of known esterification catalyst and preparing, diamides, ester-acid amide With ester-acid imide friction improver.The example of 'alpha '-hydroxy acids includes hydroxyacetic acid, lactic acid, Alpha-hydroxy dicarboxylic acids (such as winestone Acid) and/or Alpha-hydroxy tricarboxylic acids (such as citric acid), itself and amine and/or alcohol, optionally in the presence of known esterification catalyst Reaction.Be typically derived from tartaric acid, citric acid or derivatives thereof these friction improvers can derived from branched amine and/or alcohol, Generation itself has the friction improver of the branched hydrocarbyl radical of the pronounced amount being present in its structure.Improve for preparing this kind of friction The example of the suitable branching alcohol of agent includes 2-Ethylhexyl Alcohol, different tridecanol, Guerbet alcohol and its mixture.Friction improver can To be weighed with 0-6 weight % or 0.001-4 weight %, or 0.01-2 weight % or 0.05-3 weight % or 0.1-2 Amount % or 0.1-1 weight % or 0.001-0.01 weight % are present.

Other performance additive can be comprising the detersive/dispersant for replacing acylating agent containing alkyl.Acylating agent can be as a example by Such as Hydrocarbyl-substituted succinic acid, or Hydrocarbyl-substituted succinic acid and amine or the condensation product of alcohol；That is Hydrocarbyl-substituted succinic acid imide or hydrocarbon Base replaces succinate.In one embodiment, detersive/dispersant can be butanedioic acid, the acyl of polyisobutenyl replacement Amine or ester, wherein polyisobutenyl substituent have the number-average molecular weight of 100-5000.In some embodiments, detersive can Think C₆-C₁₈Substituted butanedioic acid, acid amides or ester.The more detailed description of alkyl replacement acylating agent detersive can be from September, 2011 Find in [0017th] of U.S. Publication 2011/0219674 disclosed in 15 days-[0036] section.

In one embodiment, other detersive/dispersants are the quaternary ammonium salt of those different from this technology.Other seasons Ammonium salt can be to replace acylating agent by alkyl, such as be more than 1200M with number-average molecular weight_nHydrocarbyl substituent poly- isobutyl Base amber acid or anhydride, the polyisobutyl group amber acid or anhydride with the hydrocarbyl substituent that number-average molecular weight is 300-750, or have Number-average molecular weight is 1000M_nHydrocarbyl substituent polyisobutyl group succinyl oxide prepare quaternary ammonium salt.

In one embodiment, by nitrogen-containing compound and with the hydrocarbyl substituent that number-average molecular weight is 300-750 Alkyl replaces acylation reaction and other quaternary ammonium salts for preparing are acid imide.In one embodiment, by nitrogen-containing compound and It is more than 1200M with number-average molecular weight_nHydrocarbyl substituent or with number-average molecular weight for 300-750 hydrocarbyl substituent Alkyl replace acylation reaction and the quaternary ammonium salt for preparing is acid amides or ester.

In yet another embodiment, alkyl replace acylating agent may include the monomer with 20-54 carbon atom, dimer or Trimer carboxylic acid and to primary or secondary amine in reactivity.The including but not limited to following sour monomer of suitable acid, dimer or trimerization Thing acid：Formic acid, acetic acid, propionic acid, butyric acid, octanoic acid, capric acid, laurate, myristic acid, palmitic acid, stearic acid, arachidic acid, mountain Acid, lignoceric acid, cerinic acid, myristoleic acid, palmitoleic acid, gaidic acid (sapienic acid), oleic acid, elaidic acid, 18 Carbon enoic acid (vaccenic acid), linoleic acid, trans leukotrienes, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid And DHA.

In one embodiment, imidazoles or nitrogen-containing compound of the nitrogen-containing compound of other quaternary ammonium salts for following formula：

Wherein R can be C₁-C₆Alkylidene；R₁And R₂Can C independently of one another₁-C₆Alkylene；And R₃、R₄、R₅And R₆Can be each From independently being hydrogen or C₁-C₆Alkyl.In one embodiment, R₁Or R₂May be, for example, C₁、C₂Or C₃Alkylidene.Identical or In different embodiments, R₃、R₄、R₅、R₆May be, for example, each H or C₁、C₂Or C₃Alkyl.

In other embodiments, the quaternizing agent for preparing other quaternary ammonium salts can be dialkyl sulfate, alkyl Halogen, alkyl replace carbonic ester, hydrocarbyl epoxides, carboxylate, Arrcostab or its mixture.In some cases, quaternizing agent Can be hydrocarbyl epoxides.In some cases, quaternizing agent can be the hydrocarbyl epoxides combined with acid.In some feelings Under condition, quaternizing agent can be salicylate, oxalate or terephthalate.In one embodiment, alkyl epoxidation Thing is alcohol functionalized epoxides or C₄-C₁₄Epoxides.In yet another embodiment, hydrocarbyl epoxides can be C₄-C₂₀ Epoxides.

In some embodiments, quaternizing agent is polyfunctional, is produced as being coupled other quaternary ammonium salts of quaternary ammonium salt.

Other quaternary ammonium salts have the quaternary ammonium salt of hydrophobic structure part in including but is not limited to anion.Example compound bag Include the quaternary ammonium compound with following formula：

Wherein R⁰、R¹、R²And R³Optionally substituted alkyl, thiazolinyl or aryl are each independently, and R is included with least 5 The optionally substituted hydrocarbyl moieties of individual carbon atom.

Other quaternary ammonium salts may also include polyetheramine, its be comprising at least one can quaternized tertiary amino polyethers replace amine and Tertiary amino is changed into the product of the quaternizing agent of quaternary ammonium group.

Also can by dispersant by with plurality of reagents in any one reaction and post-process.Wherein, these be urea, thiocarbamide, Dimercaptothiodiazole, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon substituted succinyl oxide, nitrile, epoxides, boron compound and phosphatization are closed Thing.The reference paper that the process is described in detail in detail is listed in United States Patent (USP) 4,654,403.

Fuel of the present invention and/or lubricant compositions can add comprising the detersive different from the acid imide quaternary ammonium salt technology Plus agent.In engine lubrication field, the most frequently used detersive (is typically based on this metalloid such as calcium, magnesium by alkaline metal-containing compound Or the metal hydroxides of sodium, oxide or carbonate) presence obtain most or all its basicity or TBN.This metalloid mistake Alkaline detersive, also referred to as parlkaline or hyperalkaline salt, usually single phase homogeneous Newtonian systems, is characterized in that tenor exceedes According in metal and the stoichiometry with the specific acidic organic compound of metal reaction and existing.Parlkaline material is usual By the mixture that makes acid material (usual inorganic acid or lower level carboxylic acid such as carbon dioxide) and acidic organic compound (also referred to as For matrix), the metal base of stoichiometric excess, generally in a kind of inert organic solvents for acid organic substrate (for example Mineral oil, naphtha, toluene, dimethylbenzene) reaction medium in reaction and prepare.Generally, also there is a small amount of accelerator, such as benzene Phenol or alcohol, and in some cases, Shao Liangshui.Acid organic substrate generally has enough carbon atom numbers to provide in oil In solubility.

This kind of conventional parlkaline material and preparation method thereof is well known to those skilled in the art.Description prepares sulfonic acid, carboxylic Acid, phenol, phosphonic acids and its patent of the technology of the alkaline metal salt of any two or more kinds of mixtures includes U.S. in these State's patent 2,501,731；2,616,905；2,616,911；2,616,925；2,777,874；3,256,186；3,384,585； 3,365,396；3,320,162；3,318,809；3,488,284；With 3,629,109.Salixarate detersives are described in U.S. In state's patent 6,200,936.In certain embodiments, detersive can include the detersive of salt containing metal salicylate, for example, cross alkali Property alkyl substituted salicylic acid calcium detersive and it is described in United States Patent (USP) 5,688,751 and 4,627,928.

Viscosity improver (otherwise referred to as viscosity index improver or viscosity improver) can be included in fuel of the present invention and/ Or in lubricant compositions.Viscosity improver is usually polymer, including polyisobutene, polymethacrylates (PMA) and poly- Methacrylate, hydrogenated diene polymer, alkyl styrenes, esterification styrene-maleic anhydride copolymer, alkyl hydrides virtue Hydrocarbon-conjugated diene copolymer and polyolefin.PMA is prepared by the mixture of the methacrylate monomers with different alkyl.Alkane Base can be the straight or branched group comprising 1-18 carbon atom.Most PMA are viscosity improver and pour-point depressant.

Also the multi-functional viscosity improver for having dispersant and/or non-oxidizability performance is known, and optionally can be used In fuel and/or lubricant compositions.Dispersant viscosity modifiers (DVM) are an example of this kind of multifunction additive. DVM generally by a small amount of nitrogen containing monomer and alkyl methacrylate copolymerization, is produced with dispersion force, viscosity modified, pour point Drop and dispersion force some combination additives and prepare.Vinylpyridine, NVP and methacrylic acid N, Example of the N '-dimethyl amino ethyl ester for nitrogen containing monomer.By gathering that one or more acrylic acid alkyl polyisocyanate polyaddition or copolymerization are obtained Acrylate also serves as viscosity improver.

Antiwear additive can be used for provided herein is fuel and/or lubricant compositions in.In some embodiments, antiwear additive May include phosphorous wear-resistant/extreme pressure agent, such as metal thiophosphate, phosphate and its salt, phosphorus-containing carboxylic acid, ester, ether and acid amides；With Phosphite.In certain embodiments, phosphorus antiwear additive can with provide 0.01-0.2 or 0.015-0.15 or 0.02-0.1 or The amount of 0.025-0.08 weight % phosphorus is present.Generally, antiwear additive is zinc dialkyl dithiophosphate (ZDP).For can include The typical ZDP of 11%P (being based on oil-free), suitable amount may include 0.09-0.82 weight %.Not phosphorous antiwear additive includes borate (including boration epoxides), dithio carbamate compounds, molybdate compound and olefine sulfide.In some embodiment party In case, fuel of the present invention and/or lubricant compositions do not contain phosphorous wear-resistant/extreme pressure agent.

Can be used for fuel of the present invention and/or the foam inhibitor in lubricant compositions include polysiloxanes, ethyl acrylate and The copolymer of 2-EHA and optional vinyl acetate；Demulsifying agent, including fluorinated silicones, trialkyl phosphate Ester, polyethylene glycol, polyethylene glycol oxide, PPOX and (ethylene oxide-propylene oxide) polymer.The technology can also with contain Silicone antifoam agent and C₅-C₁₇Alcohol combination is used together.

Can be used for fuel of the present invention and/or the pour-point depressant in lubricant compositions include polyalphaolefin, maleic anhydride- The ester of styrol copolymer, poly- (methyl) acrylate, polyacrylate or polyacrylamide.

Metal deactivator may be selected from the derivative (usual tolyl-triazole) of BTA, 1,2,4- triazoles, benzimidazole, Two thio benzothiazole of two Thiobenzimidazole of 2- alkyl or 2- alkyl, 1- amino -2- propyl alcohol, dimercaptothiodiazole it is derivative Thing, sad octylame, the condensation product of dodecenyl succinic acid or acid anhydride and/or aliphatic acid such as oleic acid and polyamines.Metal deactivator Can be described as corrosion inhibitor.

Sealing sweller includes cyclobufene sultone derivative Exxon Necton-37^TM(FN 1380) and Exxon Mineral Seal Oil^TM(FN 3200)。

Fuel composition

In some embodiments, this technology provides fuel composition.In some embodiments, fuel composition is included Most of (>50 weight %) gasoline or middle distillate fuel.In one embodiment, there is provided the combustion comprising most of diesel fuel Feed composition.

In yet another embodiment, fuel composition includes above-mentioned HMW acid imide quaternary ammonium salt and at least one anti-breast Agent.The demulsifying agent for being suitable to be used together with above-mentioned quaternary ammonium salt may include but be not limited to arylsulphonate and poly-alkoxylation Alcohol, such as polyethylene glycol oxide and polyoxypropylene copolymer etc..Demulsifying agent can also include nitrogen-containing compound, for exampleOxazoline And imidazolinium compounds, and fatty amine, and mannich compound.Mannich compound is alkylphenol and aldehyde (especially first Aldehyde) and amine (especially amine condensation product and polyalkylene polyamine) product.Material described in following United States Patent (USP) is to say Bright property：United States Patent (USP) Nos.3,036,003；3,236,770；3,414,347；3,448,047；3,461,172；3,539, 633；3,586,629；3,591,598；3,634,515；3,725,480；3,726,882；With 3,980,569, will by quoting Which is incorporated herein in.Other suitable demulsifying agents are the alkali metal or alkaline earth of such as alkyl substituted phenol-and naphthalene sulfonate Slaine, and the alkali metal or alkali salt of aliphatic acid, and neutral compound, such as such as alcohol alkoxylates, alcohol second Epoxide compound, such as phenol alcoxylates, tert-butyl phenol ethoxylate and tert-amyl phenol ethoxylate, fat The condensation product of acid, alkylphenol, ethylene oxide (EO) and propylene oxide (PO), such as including the form of Pluronic PE 6800, Polyethyleneimine or polysiloxanes.Any commercially available demulsifying agent can suitably be enough in fuel provide 5-50ppm process The amount of rate is used.In one embodiment, fuel composition of the present invention does not include demulsifying agent.Demulsifying agent can individually or group Close and use.Some demulsifying agents are for example commercial by Nalco or Baker Hughes.The exemplary process rate of demulsifying agent and fuel can Think the 0-50ppm of fuel gross weight, or 5-50ppm, or 5-25ppm, or 5-20ppm.

The technology can be also made together with the demulsifying agent of the replaced by 2-carboxylic acid alkyl comprising free acid form or acid anhydride form Can be intramolecular acid anhydride with, the acid anhydride, such as succinyl oxide, glutaric anhydride or phthalic anhydride, or by two dicarboxylic acids The molecule intramolecular anhydride that molecule links together.Hydrocarbyl substituent can have 12-2000 carbon atom, and may include with 300- The polyisobutenyl substituent of 2800 number-average molecular weight.The replaced by 2-carboxylic acid alkyl of example is including but not limited to derived from the third two Acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, neighbour The hydrocarbon of phthalic acid, M-phthalic acid, terephthalic acid (TPA), o-, m- or p- phenylenediacetic Acid, maleic acid, fumaric acid or glutaconate Base replaces acid.

In another embodiment, fuel composition comprising the technology acid imide quaternary ammonium salt and other detersives/point Powder.Conventional detersive/dispersant additives are preferably with the hydrophobic of at least one number-average molecular weight with 100-10000 Property alkyl and at least one polar moieties amphiphilic species, the polar moieties selected from (i) with most 6 nitrogen The mono amino or polyamino of atom, at least one nitrogen-atoms have alkaline performance；(ii) there is alkalescence with least one nitrogen-atoms The mono amino of performance or the hydroxyl of polyamino combination；(iii) carboxyl or its alkali metal or alkali salt；(iv) sulfonic acid group or Its alkali metal or alkali salt；(v) by hydroxyl, at least one nitrogen-atoms have alkaline performance mono amino or polyamino or Polyoxy-the C blocked by carbamate groups₂-C₄Alkylene moiety；(vi) carboxylate group；(vii) derived from amber Acid anhydrides and the structure division with hydroxyl and/or amino and/or acylamino- and/or acylimino；And/or (viii) is by replacing The structure division that the Mannich reaction of phenol and aldehyde and monoamine or polyamines is obtained.

Guarantee that the hydrophobicity alkyl in the above detersive/dispersant additives of the suitable solubility in fuel has Number-average molecular weight (the M of 85-20,000,100-10,000 or 300-5000_n).In yet another embodiment, detersive/dispersant Additive has the M of 300-3000,500-2500,700-2500 or 800-1500_n.Typical hydrophobicity alkyl can be with Number-average molecular weight M of 300-5000,300-3000,500-2500 or 700-2500_nPolypropylene-base, polybutylene-based and poly- isobutyl Thiazolinyl.In one embodiment, detersive/dispersant additives have the M of 800-1500_n。

Other performance additive can include the nitrogenous detersive/dispersants of high TBN, and such as succinimide, i.e. alkyl replace The condensation product of succinyl oxide and poly- (alkylene amines).Succinimide detersive/dispersant is described more fully below in United States Patent (USP) In 4,234,435 and 3,172,892.Another kind of ashless dispersant is by alkyl acylating agent and multi-aliphatic alcohol such as glycerine, season The high-molecular weight ester that penta tetrol or D-sorbite react and prepare.This kind of material is described in greater detail in United States Patent (USP) 3,381, In 022.

Nitrogenous detersive can be the product of the derivative acylating agent of carboxylic acid and amine.Acylating agent can be spread out by formic acid and its acylation The biological acylating agent change to the high molecular weight aliphatic substituent with most 5,000,10,000 or 20,000 carbon atoms.Ammonia Based compound can be by ammonia itself to generally with the aliphatic substituent of at most 30 carbon atoms and the change of the amine of at most 11 nitrogen-atoms Change.Acylated amino compounds suitable for the present invention can be by the acyl with least hydrocarbyl substituent of 8 carbon atoms Agent with comprising at least one primary or secondary amino compound reaction and formed those.Acylating agent can be monocarboxylic acid or poly- carboxylic Sour (or its reactive equivalent), for example, replace butanedioic acid, phthalic acid or propionic acid, and amino-compound can be polyamines or The mixture of the mixture of polyamines, such as ethylene.Alternatively, amine can be hydroxyalkyl substituted polyamines.This kind of acylation Hydrocarbyl substituent in agent can include at least 10 carbon atoms.In one embodiment, hydrocarbyl substituent can include at least 12, Such as 30 or 50 carbon atoms.In yet another embodiment, it may comprise up to 200 carbon atoms.The alkyl of acylating agent replaces Base can have 170-2800, the number-average molecular weight (M of such as 250-1500_n).In other embodiments, the M of substituent_nCan be with For 500-1500, or alternatively 500-1100.In yet another embodiment, the M of substituent_nCan be 700-1300. In another embodiment, hydrocarbyl substituent can have 700-1000, or the number-average molecular weight of 700-850 or such as 750.

Another kind of ashless dispersant is Mannich base.These are many by higher molecular weight alkyl substituted phenol, alkylidene Amine and aldehyde, such as formaldehyde condensation and the material that formed and United States Patent (USP) 3 is described in greater detail in, in 634,515.

Useful nitrogenous dispersant includes (a) aldehyde, and (b) Mannich reaction between polyamines and (c) optionally substituted phenol is produced Thing.Phenol can be substituted the molecular weight that Mannich product is had less than 7500.Optionally, molecular weight can be less than 2000, Less than 1500, less than 1300, or e.g., less than 1200, less than 1100, less than 1000.In some embodiments, Mannich Product has less than 900, less than 850, or less than 800, less than 500, or the molecular weight less than 400.Fortified phenol can be By at most 4 substituent groups on aromatic ring.For example, it can be three or disubstituted benzenes phenol.In some embodiments, phenol can be with For monosubstituted phenol.Replace can it is adjacent and/or and/or contraposition on.To form Mannich product, aldehyde is 4 with the mol ratio of amine: 1-1:1 or 2:1-1:1.Aldehyde can be at least 0.75 with the mol ratio of phenol:1；It is preferred that 0.75:1-4:1, preferably 1:1-4:1, more It is preferred that 1:1-2:1.To form preferred Mannich product, phenol is preferably at least 1.5 with the mol ratio of amine:1, more preferably at least 1.6:1, more preferably at least 1.7:1, for example, at least 1.8:1, preferably at least 1.9:1.Phenol can be at most with the mol ratio of amine 5:1；For example it can be at most 4:1, or at most 3.5:1.Suitably, it is at most 3.25:1st, at most 3:1st, at most 2.5: 1st, at most 2.3:1 or at most 2.1:1.

Other dispersants include polymeric dispersant additive, it typically is comprising polar functional to give polymer dispersion The hydrocarbyl polymers of force characteristic.Amine is commonly used for preparing the nitrogenous dispersants of high TBN.One or more poly- (alkylidene can be used Amine), and these can include one or more poly- (alkylene amines) with 3-5 ethylene units and 4-6 nitrogen unit.It is this kind of Material includes trien (TETA), tetren (TEPA) and penten (PEHA).This kind of material leads to Frequently as comprising a series of ethylene oxide units and the various isomers of nitrogen-atoms numbers purpose and various isomer structures including each The mixture for planting circulus is commercially available.Poly- (alkylene amines) are referred to as the residual relatively high score of ethylene amines kettle in can also including industry Son amount amine.

In one embodiment, fuel composition can also include the quaternary ammonium different from acid imide quaternary ammonium salt described herein Salt.Other quaternary ammonium salts can be included：(a) comprising (i) at least one tertiary amino as described above and (ii) with 100-5000, or 250-4000, or the compound of the hydrocarbyl substituent of the number-average molecular weight of 100-4000 or 100-2500 or 3000；(b) such as It is suitable to the tertiary amino of (a) (i) is changed into the quaternizing agent of quaternary nitrogen described in upper.Other quaternary ammonium salts are more thoroughly described in 2011 United States Patent (USP) Nos.7 that May 31 submitted to, the 8 of the submission of on December 27th, 951,211 and 2011,083814, and 2013 years 5 2012/0010112,2013 5 disclosed in U.S. Publication Nos.2013/0118062,12 days January in 2012 disclosed in the moon 16 Disclosed in September, 2008/0113890 and 2011 disclosed on May 15th, 2013/0133243,2008 disclosed in months 30 days 15 days 2011/0219674th, US 2013/ disclosed in Augusts in 2012/0149617,2013 of US disclosed in 14 days Mays in 2012 29 days 0225463rd, the US 2011/ disclosed on December 29, in 2011/0258917,2011 of US disclosed in 27 days October in 2011 0315107th, the US 2012/ disclosed on October 11, in 2013/0074794,2012 of US disclosed in 28 days March in 2013 0255512nd, the US 2013/ disclosed on May 16, in 2013/0333649,2013 of US disclosed in 19 days December in 2013 International Publication WO disclosed in 17,0118062 and 2011 on November is disclosed disclosed in Nos.2011/141731, August 11 in 2011 WO 2013/070503 disclosed in May 16 in 2013/017886,2013 disclosed in 7 days 2 months 2011/095819 and 2013 year, 2 months 2011/110860,2013 WO disclosed in 7 days of WO disclosed in 15 days December in 2011 2 months 2013/017889,2013 In WO 2013/017884 disclosed in 7 days.

Can be that acylating agent is replaced by alkyl different from other quaternary ammonium salts of the present invention, such as be big with number-average molecular weight In 1200M_nHydrocarbyl substituent polyisobutyl group amber acid or anhydride, with number-average molecular weight for 300-750 hydrocarbyl substituent Polyisobutyl group amber acid or anhydride, or have number-average molecular weight be 1000M_nHydrocarbyl substituent polyisobutyl group butanedioic acid or Quaternary ammonium salt prepared by acid anhydride.

In one embodiment, the fuel composition comprising quaternary ammonium salt of the present invention can further include other quaternary ammonium salts. Other salt can be to be acylated with replacing for the alkyl of the hydrocarbyl substituent of 1300-3000 with number-average molecular weight by nitrogen-containing compound The acid imide that agent is reacted and prepared.In one embodiment, by nitrogen-containing compound with number-average molecular weight be more than 1200M_nHydrocarbyl substituent or with number-average molecular weight for 300-750 hydrocarbyl substituent alkyl replace acylation reaction And the quaternary ammonium salt for preparing is acid amides or ester.

Alkyl replace acylating agent can also be by it is at least one be the ethylenically unsaturated hydrocarbons with 2-100 carbon atom Monomer copolymerization and the copolymer that formed.Monomer can be linear, branched or ring-type.Monomer can have oxygen or nitrogen substituent, but Do not react with amine or alcohol.Monomer can be reacted with the second comonomer for the carboxylic acid with 3-12 carbon atom or carboxylic acid derivates.The Two monomers can have one or two carboxylic acid functional and to amine or alcohol in reactivity.When being prepared using the method, alkyl takes There is number-average molecular weight M of 500-20,000 for acylating agent copolymer_n。

Alternatively, it can be terpolymer that alkyl replaces acylating agent, and which is ethene and at least one is with least The monomer of the ethylenically unsaturated monomer of one tertiary N atom, the aliphatic series list carboxylic one or more with (i) with 1-24 carbon atom The product of the Arrcostab of alkenyl esters or (ii) acrylic or methacrylic acid of acid.

In one embodiment, the nitrogen-containing compound of other quaternary ammonium salts is the nitrogenous chemical combination of in imidazoles or following formula Thing：

Wherein R can be C₁-C₆Alkylidene；R₁And R₂C can be each independently₁-C₆Alkylene；And R₃、R₄、R₅And R₆Can Hydrogen or C independently of one another₁-C₆Alkyl.In one embodiment, R₁Or R₂Can be such as C₁、C₂Or C₃Alkylidene.Identical Or in different embodiments, each R₃、R₄、R₅、R₆Can be such as H or C₁、C₂Or C₃Alkyl.

In other embodiments, the quaternizing agent for preparing other quaternary ammonium salts can be dialkyl sulfate, alkyl Halogen, alkyl replace carbonic ester, hydrocarbyl epoxides, carboxylate, Arrcostab or its mixture.In some cases, quaternizing agent Can be hydrocarbyl epoxides.In some cases, quaternizing agent can be the hydrocarbyl epoxides combined with acid.In some feelings Under condition, quaternizing agent can be salicylate, oxalate or terephthalate.In one embodiment, alkyl epoxidation Thing can be alcohol functionalized epoxides or C₄-C₁₄Epoxides.

The exemplary process rate of other detersive/dispersants and fuel of the present invention is 0-500ppm, or 0-250ppm, or 0-100ppm, or 5-250ppm, or 5-100ppm, or 10-100ppm.

In one particular embodiment, acid imide quaternary ammonium salt of the fuel composition comprising this technology and cold flow improver. Cold flow improver is generally selected from (1) C₂-C₄₀The copolymer of alkene and at least one other ethylenically unsaturated monomers；(2) combed is gathered Compound；(3) polyoxyalkylene；(4) polar nitrogen compounds；(5) sulfo group carboxylic acid or sulfonic acid or derivatives thereof；(6) poly- (methyl) third Olefin(e) acid ester.Can use in particular category (1)-(6) class the different mixtures for representing or from different classes of (1)- (6) mixture of representative.

For the copolymer of classification (1), suitable C₂-C₄₀Olefinic monomer is for for example with 2-20, especially 2-10 carbon Atom, and 1-3, especially preferably 1 or 2 carbon-to-carbon double bond, those with a carbon-to-carbon double bond.In the case of the latter, Carbon-to-carbon double bond can end (alhpa olefin) or internal arrangement.It is preferable, however, that alhpa olefin, the more preferably alhpa olefin with 2-6 carbon atom, Such as propylene, 1- butylene, 1- amylenes, particularly 1- hexenes and ethene.At least one other olefinic of classification (1) is unsaturated single Body is preferably selected from alkenyl carboxylate；Such as C of the carboxylic acid with 2-21 carbon atom₂-C₁₄Alkenyl esters, such as vinyl and propylene Base ester, its alkyl can be for linear or branched, in these, optimal ethylene base ester, and the example of suitable alkenyl carboxylate is It is vinyl acetate, propionate, vinyl butyrate, 2 ethyl hexanoic acid vinyl acetate, new vinyl acetate acid, vinyl caproate, new Vinyl pelargonate ester, vinyl neodecanoate and corresponding propylene, (methyl) acrylate；Such as (methyl) acrylic acid and C₁-C₂₀ Alkanol, especially C₁-C₁₀Alkanol, particularly with methyl alcohol, ethanol, propyl alcohol, isopropanol, n-butanol, sec-butyl alcohol, isobutanol, The ester of the tert-butyl alcohol, amylalcohol, hexanol, enanthol, octanol, 2-Ethylhexyl Alcohol, nonyl alcohol and decyl alcohol and its constitutional isomer and other alkene； Preferred molecular weight is higher than above-mentioned C₂-C₄₀Alkylene monomer, such as alkylene monomer used are ethene or propylene, suitably other alkene Hydrocarbon monomer is particularly C₁₀-C₄₀Alhpa olefin.

The suitable copolymer of classification (1) also includes that of two or more different alkenyl carboxylates of copolymerized form A bit, the alkenyl carboxylate is different in terms of alkenyl functional and/or hydroxy-acid group.It is suitable to also have in addition to alkenyl carboxylate, bag The copolymer of at least one alkene containing copolymerized form and/or at least one (methyl) acrylate.

C₂-C₄₀The C of alhpa olefin, the olefinic unsaturated monocarboxylic with 3-15 carbon atom₁-C₂₀Arrcostab and have 2-21 The C of the saturation monocarboxylic acid of individual carbon atom₂-C₁₄The terpolymer of alkenyl esters is also suitable the copolymer for making classification (K1).This three Membered copolymer is described in WO 2005/054314.Typical this terpolymer by ethene, 2-EHA and Vinyl acetate is formed.

At least one or other ethylenically unsaturated monomers are in the copolymer of classification (1) with based on the preferred 1-50 of total copolymer The amount copolymerization of weight %, especially 10-45 weight %, particularly 20-40 weight %.Therefore, according in the copolymer of classification (1) The major part of the weight of monomeric unit generally originates from C₂-C₄₀Base alkene.The copolymer of classification (1) can have 1000-20,000, More preferably 1000-10, number-average molecular weight M of 000, particularly 1000-8000_n。

It is unsaturated with another olefinic single that the typical comb-shaped polymer of component (2) can for example pass through maleic anhydride or fumaric acid Body, such as with alkene or beta-unsaturated esters such as vinyl acetate copolymerization, subsequently by acid anhydride or sour sense with least 10 carbon atoms Alcohol esterification and obtain.Other suitable comb-shaped polymers be alhpa olefin and esterification comonomer copolymer, for example styrene and The esterified copolymer or styrene and the esterified copolymer of fumaric acid of maleic anhydride.Suitable comb-shaped polymer can also be poly- Fumarate or poly ester.The homopolymers and copolymer of vinyl ethers is also suitable comb-shaped polymer.It is suitable for classification (2) comb-shaped polymer of component for example also has WO 2004/035715 and " Comb-Like Polymers.Structure And Properties ", N.A.Plat é and V.P.Shibaev, J.Poly.Sci.Macromolecular Revs.8, the Described in 117-253 page (1974) those.The mixture of comb-shaped polymer is also suitable.

The polyoxyalkylene for being suitable for classification (3) is such as polyoxyalkylene esters, polyoxyalkylene ether, mixing polyoxyalkylene esters/ether And its mixture.These polyoxyalkylene compounds preferably comprise at least one linear alkyl each with 10-30 carbon atom, Preferably at least 2 linear alkyls, and the polyalkylene oxide groups of the number-average molecular weight with most 5000.It is suitable polyoxyalkylenated Compound is described in such as EP-A061895 and United States Patent (USP) No.4,491,455.Specific polyoxyalkylene compounds are based on to be had The polyethylene glycol and polypropylene glycol of the number-average molecular weight of 100-5000.The suitable also aliphatic acid with 10-30 carbon atom Such as stearic acid or the polyoxyalkylene monoesters and diester of behenic acid.

The polar nitrogen compounds for being suitable for the component of classification (4) can be ion or non-ionic, and can have at least One substituent or at least two substituents, the substituent are formula>NR⁷Tertiary N atom form, wherein R⁷For C₈- C₄₀Alkyl.Nitrogen substituent can also be for quaternized, as cationic form.The example of this kind of nitrogen compound be ammonium salt and/or Acid amides, which can pass through at least one amine replaced by least one alkyl and the carboxylic acid or suitable with which with 1-4 carboxyl Derivatives reaction and obtain.Amine can include at least one linear C₈-C₄₀Alkyl.It is suitable to prepare the primary of the polar nitrogen compounds Amine is such as octylame, nonyl amine, decyl amine, undecylamine, lauryl amine, tetradecy lamine and higher line homologue.It is suitable to the secondary amine of the purpose For such as two-octadecylamine and methyl mountain amine.Be suitable to the purpose also has amine blends, particularly can obtain on an industrial scale Amine blends, such as fatty amine and hydrogenated tallow amine, such as such as Ullmann's Encyclopedia of Industrial Chemistry, the 6th edition, chapters and sections " Amines, aliphatic " are described.The acid for being suitable to react is such as hexamethylene -1,2- dicarboxyls Acid, cyclohexene -1,2- dicarboxylic acids, pentamethylene -1,2- dicarboxylic acids, naphthalene dicarboxylic acids, phthalic acid, M-phthalic acid, to benzene two Formic acid, and the butanedioic acid replaced by long chain hydrocarbon groups.

Sulfo group carboxylic acid, sulfonic acid of the cold flow improver of classification (5) or derivatives thereof are suitable for for such as oil-soluble carboxylic acid amides With the carboxylate of o- sulfosalicylic acid, wherein sulfonic acid sense as with alkyl replace ammonium cation sulfonate exist, such as Described in EP-A 261957.

Poly- (methyl) acrylate for being suitable for the cold flow improver of classification (6) is acrylate and methacrylate Homopolymers or copolymer.It is preferred that the copolymer of different at least two different (methyl) acrylate in terms of esterifying alcohol.Copolymerization Thing optionally other different ethylenically unsaturated monomers comprising copolymerized form.The weight average molecular weight of polymer can be 50,000- 500,000.Polymer can be methacrylic acid and saturation C₁₄And C₁₅The copolymer of the methacrylate of alcohol, acid groups quilt Hydrogenated tallow amine is neutralized.Suitable poly- (methyl) acrylate is described in such as WO 00/44857.

The mixture of cold flow improver or different cold flow improver is with preferred 0-5000 weight ppm, or 10-5000 weight Ppm, or 20-2000 weight ppm, or 50-1000 weight ppm, or 100-700 weight ppm, such as 200-500 weight The total amount of ppm add in distillate fuel or diesel fuel.

Engine oil lubricants

In different embodiments, this technology provides the engine oil lubricating composition that can be used for internal combustion engine.Internal combustion engine Can be spark ignition or compression ignition.Internal combustion engine can be two-stroke or four-stroke engine.Internal combustion engine can be car Engine, LD-diesel, large diesel engine, motorcycle engine or two-stroke or four-stroke marine diesel.Generally, it is interior Combustion engine can be bus engine or heavy-duty diesel oil internal combustion engine.

In one embodiment, in addition to the quaternary ammonium salt of this technology, inventive engine oil lubricant composition was included Alkalescence contains metal detergent or its mixture.

Overbased detergent is as known in the art.Parlkaline material, also referred to as parlkaline or hyperalkaline salt, usually Single phase homogeneous system, is characterized in that tenor more than the change according to metal and with the specific acidic organic compound of metal reaction Learn metering neutralization to exist.Parlkaline material passes through acid material (usual inorganic acid or low-grade carboxylic acid, usual carbon dioxide) With comprising acidic organic compound, reaction medium, the metal foundation thing of stoichiometric excess and accelerator for example calcium chloride, acetic acid, The mixture of phenol or alcohol reacts and prepares, and the reaction medium is comprising at least one lazy for the acidic organic material Property organic solvent (mineral oil, naphtha, toluene, dimethylbenzene etc.).Acidic organic material generally has enough carbon atom numbers To provide the solubility in oil.The amount (stoichiometrically) of " excess " metal is generally according to metal than representing.Term " metal Than " for metal total yield and the equivalents of acidic organic compound ratio.Neutral metal salt is with 1 metal ratio.With with The salt of 4.5 times of as many metals being present in normal salt has the excess of 3.5 equivalents or 4.5 ratio.Term " metal ratio " Also explain that the standard in entitled " Chemistry and Technology of Lubricants " is taught book, the 3rd edition, R.M.Mortier and S.T.Orszulik are edited, version in 2010, page 219, in subtitle 7.25.

Parlkaline is may be selected from without thiophenol salt, sulfur-bearing phenates, sulfonate, salixarate, salicylic acid containing metal detergent Salt, carboxylate and its mixture, or its boration equivalent.Overbased detergent can be with the such as Boric acid boron acidifying of boric acid agent.

Overbased detergent can be without thiophenol salt, sulfur-bearing phenates, sulfonate or its mixture.

Engine oil lubricants are can further include with 0.01 weight % to 0.9 weight %, or 0.05 weight % is to 0.8 Weight %, or 0.1 weight % to 0.7 weight %, or 0.2 weight % is clear to the overbased sulfonates that 0.6 weight % is present Net agent.

Overbased sulfonates detersive can be with 12 to less than 20, or 12-18, or 20-30, or the gold of 22-25 Category ratio.

In addition to overbased sulfonates, engine oil lubricants composition can also include one or more detersive.

Overbased sulfonates generally have 250-600, or the total base number of 300-500 (being based on oil-free).Parlkaline is peace and quiet Agent is as known in the art.In one embodiment, sulfonate detergent can be with the main of at least 8 metal ratio Linear alkyl benzene sulfonate detersive, such as U.S. Patent application 2005065045 (and authorize US 7,407,919) [0026]-[0037] described in section.Linear alkyl benzene can with linear chain Anywhere, generally at 2,3 or 4 or its mixing The phenyl ring connected on thing.Dominant linear alkylbenzenesulfonate detersive can be used in particular for help and improve fuel economy.At one In embodiment, sulfonate detergent can be the slaine of one or more oil-soluble alkyl benzene sulphonate salt compound, such as beautiful Described in [0046th] of state's patent application 2008/0119378-[0053] section.

In one embodiment, overbased sulfonates detersive includes overbased calcium sulfonate.Calcium sulfonate detergents can have There are the metal ratio and the TBN of 300-500 or 325-425 of 18-40.

Other detersives can have metal.May also include with mixed surfactant system formation containing metal detergent " mixing " detersive, the system include phenates and/or sulfonate component, for example phenates/salicylate, sulfonate/phenates, sulphur Hydrochlorate/salicylate, sulfonate/phenates/salicylate, such as such as United States Patent (USP) 6,429,178；6,429,179；6,153, 565；With described in 6,281,179.If for example using mixing sulfonate/phenate detergents, then it is assumed that mix detersive and be equal to point Yin Ru not the phenates of similar quantity and the independent phenates of sulfonate soap and the amount of sulfonate detergent.

Other detersives can have alkali metal, alkaline-earth metal or zinc counter ion counterionsl gegenions.In one embodiment, metal can be with For sodium, calcium, barium or magnesium.Generally, other detersives can be that the detersive containing sodium, calcium or magnesium is (generally, clear containing calcium or magnesium Net agent).

Other detersives typically sodium of phenates, sulfur-bearing phenates, salixarate and salicylate, calcium or magnesium salts Overbased detergent.The total base number of parlkaline phenates and salicylate generally with 180-450TBN (being based on oil-free).

Phenate detergents are typically derived from p- hydrocarbylphenol.This kind of alkylphenol can be coupled and cross alkalization with sulphur, with aldehyde idol Join and cross alkalization.Or carboxylation is forming salicylate detergent.Suitable alkylphenol includes the oligomer with propylene, i.e., four Acrylic phenol (i.e. p- dodecyl phenol or PDDP) and five acrylic phenol it is alkylating those.Other suitable alkyl Phenol is included with alhpa olefin, isomerisation of alpha alkene and polyolefin such as polyisobutylene alkylate.In one embodiment, moisten Sliding composition is comprising less than 0.2 weight %, or is less than 0.1 weight %, or even less than 0.05 weight % derived from The phenate detergents of PDDP.In one embodiment, it not is the phenate detergents derived from PDDP that lubricant compositions are included.

Overbased detergent can be with 0 weight % to 10 weight %, or 0.1 weight % to 10 weight %, or 0.2 weight Weight % of % to 8 is measured, or 0.2 weight % is present to 3 weight %.For example in large diesel engine, detersive can be with lubrication 2 weight % of agent composition are present to 3 weight %.For bus engine, detersive can be with 0.2 weight of lubricant compositions Amount weight % of % to 1 is present.In one embodiment, engine oil lubricants composition can have at least comprising at least one The overbased detergent of 3, or at least 8, or at least 15 metal ratio.

In one embodiment, the engine oil lubricants composition of the acid imide quaternary ammonium salt comprising this technology can enter one Step includes dispersant or its mixture.Dispersant may be selected from succinimide dispersants, Mannich dispersant, succinimide point Powder, polyalkylene succinic acid esters, acid amides or ester-acid amide or its mixture.

In one embodiment, engine oil lubricants composition includes dispersant or its mixture.Dispersant can be made Exist for single dispersant.Dispersant can be present as the mixture of two or more (usual 2 or 3 kind) difference dispersants, Wherein at least one can be succinimide dispersants.

Succinimide dispersants can be derived from aliphatic polyamines or its mixture.Aliphatic polyamines can be aliphatic polyamines, example Such as ethylene, propylidene polyamines, butylidene polyamines or its mixture.In one embodiment, aliphatic polyamines can be Ethylene.In one embodiment, aliphatic polyamines may be selected from ethylenediamine, diethylenetriamines, trien, four Five amine of ethylidene, penten, polyamines kettle be residual and its mixture.

In one embodiment, dispersant can be polyalkylene succinic acid esters, acid amides or ester-acid amide.For example, polyolefin Succinate can be the polyisobutylene succinic acid ester or its mixture of pentaerythrite.Polyalkylene succinic acid ester-amide can be The polyisobutylene succinic acid reacted with alcohol (such as pentaerythrite) and amine (such as diamines, usual diethylidene amine).

Dispersant can replace long chain alkenyl succinimides for N-.N- replace long chain alkenyl succinimides example be Polyisobutenyl succinimide.Generally, the polyisobutene that can derive polyisobutylene succinic anhydride has 350-5000, or The number-average molecular weight of 550-3000 or 750-2500.Succinimide dispersants and its preparation are disclosed in such as United States Patent (USP) 3, 172,892、3,219,666、3,316,177、3,340,281、3,351,552、3,381,022、3,433,744、3,444, 170th, 3,467,668,3,501,405,3,542,680,3,576,743,3,632,511,4,234,435, Re 26,433 and 6, 165,235th, in 7,238,650 and EP patent application, 0 355 895 A.

Also can by dispersant by conventional method by with plurality of reagents in any one reaction and post-process.Wherein, this Be boron compound (such as boric acid), urea, thiocarbamide, dimercaptothiodiazole, carbon disulfide, aldehyde and ketone, carboxylic acid such as terephthalic acid (TPA) a bit, Hydrocarbon substituted succinyl oxide, maleic anhydride, nitrile, epoxides and phosphorus compound.In one embodiment, post-processing dispersant is Boration.In one embodiment, post-process dispersant to react with dimercaptothiodiazole.In one embodiment, Post processing dispersant can be with phosphoric acid or phosphorous acid reaction.In one embodiment, post-processing dispersant can be with terephthalic acid (TPA) With acid reaction (as described in U.S. Patent application US2009/0054278).

In one embodiment, dispersant can be boration or non-boration.Generally, borated dispersants can be with For succinimide dispersants.In one embodiment, ashless dispersant can be boracic, i.e., with the boron for combining and The boron is provided to lubricant compositions.Boron-containing dispersant can be being supplied to lubricant compositions at least 25ppm boron, at least The amount of 50ppm boron or at least 100ppm boron is present.In one embodiment, lubricant compositions can be free of boracic dispersion Agent, that is, be supplied to final preparaton to be not more than 10ppm boron.

Dispersant can be prepared/be obtained/be obtained by the reaction of succinyl oxide by " alkene " or " heat " reaction, and which can be described as " direct alkylation method "." alkene " reaction mechanism and General reactions condition are summarized in B.C.Trivedi and B.C.Culbertson Editor " maleic anhydride " published in nineteen eighty-two by Plenum Press, in the 147-149 page.By what is reacted including " alkene " Dispersant prepared by method can be that with being present in less than 50 moles of %, or 0 to less than 30 moles of %, or 0 to being less than The polyisobutenyl succinimide of the carbocyclic ring on 20 moles of %, or 0 mole of % dispersant molecule." alkene " reaction can have 180 DEG C to being less than 300 DEG C, or 200 DEG C to 250 DEG C, or 200 DEG C to 220 DEG C of reaction temperature.

Dispersant can also be obtained by chlorine householder method/is obtained, and methods described is usually directed to Deere this Alder chemistry, leads Cause forms carbocyclic ring key.The method is well known by persons skilled in the art.Chlorine householder method can be produced as having and be present in 50 and rub The dispersant of the polyisobutenyl succinimide of the carbocyclic ring on your % or more, or 60-100 mole of % dispersant molecule.Heat United States Patent (USP) 7 is described in greater detail in chlorine householder method, 615,521,4-5 hurdles and prepare in embodiment A and B.

Dispersant can have 5:1-1:10、2:1-1:10, or 2:1-1:5, or 2:1-1:2 carbonyl:Nitrogen ratio (CO:N Than).In one embodiment, dispersant can have 2:1-1:10, or 2:1-1:5, or 2:1-1:2, or 1:1.4- 1:0.6 CO:N ratios.

In one embodiment, dispersant can be succinimide dispersants, it may include polyisobutene succinic acyl is sub- Amine, wherein the polyisobutene for deriving polyisobutenyl succinimide has 350-5000, or the equal molecule of number of 750-2500 Amount.Dispersant can be with 0 weight % of lubricant compositions to 20 weight %, 0.1 weight % to 15 weight %, or 0.5 weight Amount weight % of % to 9, or 1 weight % to 8.5 weight % or the presence of 1.5-5 weight %.

In one embodiment, the engine oil lubricants composition of the acid imide quaternary ammonium salt comprising this technology can be The lubricant compositions of molybdenum compound are included further.Molybdenum compound can be antiwear additive or antioxidant.Molybdenum compound is optional From molybdenum dialkyl-dithiophosphate, molybdenum dithiocarbamate, the salt of molybdenum compound and its mixture.Molybdenum compound is provided to Lubricant compositions 0-1000ppm, or 5-1000ppm, or 10-750ppm, 5ppm to 300ppm, or 20ppm is extremely 250ppm molybdenums.

In another embodiment, the engine oil lubricants composition of the quaternary ammonium salt comprising this technology can further include Antioxidant.Antioxidant includes olefine sulfide, diaryl amine, alkylation diaryl amine, hindered phenol, molybdenum compound (such as two Thiocarbamic acid molybdenum), hydroxy thioether or its mixture.In one embodiment, lubricant compositions include antioxidant Or its mixture.Antioxidant can be with 0 weight % of lubricant compositions to 15 weight %, or 0.1 weight % is to 10 weights %, or 0.5 weight % to 5 weight %, or 0.5 weight % to 3 weight % are measured, or 0.3 weight % is deposited to 1.5 weight % .

In one embodiment, the engine oil lubricants composition of the acid imide quaternary ammonium salt comprising this technology is further Comprising phenols or amine antioxidants or its mixture, and wherein antioxidant is with 0.1 weight % to 3 weight %, or 0.5 weight Weight % of % to 2.75 is measured, or 1 weight % is present to 2.5 weight %.

Diaryl amine or alkylation diaryl amine can be PA (PANA), alkylated diphenylamine or alkylation Nonox or its mixture.Alkylated diphenylamine may include two-nonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine, Two-octylated diphenylamine, two-decylated diphenylamine, decyl diphenylamine and its mixture.In one embodiment, diphenylamines May include nonyl diphenylamine, dinonyldiphenylamine, octyl diphenylamine, dioctyl diphenylamine or its mixture.In an embodiment party In case, alkylated diphenylamine may include nonyl diphenylamine or dinonyldiphenylamine.Alkylation diaryl amine may include octyl group, two- Octyl group, nonyl, two-nonyl, decyl or two-decyl phenyl naphthylamines.

Hindered phenol antioxidant usually contains sec-butyl and/or the tert-butyl group as steric group.Phenyl can further by hydrocarbon Base (generally linear or branched-alkyl) and/or the bridge linkage group being connected on the second aromatic group replace.Suitable hindered phenol antioxygen The example of agent includes 2,6- di-t-butyl phenol, 4- methyl -2,6- di-t-butyl phenol, 4- ethyl -2,6- di-t-butyls Phenol, 4- propyl group -2,6- di-t-butyls phenol or 4- butyl -2,6- di-t-butyls phenol or 4- dodecyl two-uncles of -2,6- Butylphenol.In one embodiment, hindered phenol antioxidant can be ester, and may include for example from Ciba's IrganoxTML-135.Suitable hindered phenol antioxidant containing ester is chemical to be described in more detail in United States Patent (USP) 6,559,105 Find.

The example that can be used as the molybdenum dithiocarbamate of antioxidant includes the commercial materials sold with trade name, for example From the Molyvan of R.T.Vanderbilt Co., Ltd.sA and855, and Adeka Sakura-Lube^TMS-100, S-165, S-600 and 525, or its mixture.

In one embodiment, the engine oil lubricants composition of the acid imide quaternary ammonium salt comprising this technology is further Comprising viscosity improver.Viscosity improver is as known in the art, and may include hydrogenated styrene-butadiene rubber, second The ethylene copolymer of alkene-propylene copolymer and propylene and higher alkene, polymethacrylates, polyacrylate, hydrogenation of benzene second Alkene-isoprene copolymer, hydrogenated diene polymer, alkyl styrenes, polyolefin, the ester of maleic anhydride-olefin copolymer (such as those described in international application WO 2010/014655), the ester of maleic anhydride-styrene copolymers, or its mixture.It is viscous Degree modifier may include block copolymer, and the block copolymer is included：(i) vi-ny l aromatic monomers block, and (ii) conjugation It is diene olefin monomer block (such as hydrogenated styrene-butadiene copolymer or hydrogenated styrene isoprene copolymer), poly- Methacrylate, ethylene-alpha-olefin copolymer, the hydrogenation comprising conjugate diene monomer such as butadiene or isoprene are star-like poly- Compound, or the star-type polymer or its mixture of polymethacrylates.

In one embodiment, viscosity improver can be dispersant viscosity modifiers.Dispersant viscosity modifiers can Including functionalised polyolefin, such as with acylating agent such as maleic anhydride and amine-functionalized ethylene-propylene copolymer.

In one particular embodiment, dispersant viscosity modifiers are included further with dispersant amine groups functionalization Olefin copolymer.Generally, olefin copolymer is ethylene-propylene copolymer.Olefin copolymer has a 5000-20, and 000, or 6000-18,000, or 7000-15,000 number-average molecular weight.Olefin copolymer can have to be cut by Orbahn as described above Cut test (ASTM D6278) and be measured as 0-20, or 0-10, or the shear stability index of 0-5.

The formation of dispersant viscosity modifiers is well known in the art.Dispersant viscosity modifiers may include such as U.S. Patent US 7,790,661, the 48th row of the 2nd hurdle to described in the 38th row of the 10th hurdle those.

In one embodiment, dispersant viscosity modifiers can graft on 15-80 by olefin carboxylic acid's acylating agent and rub You are % ethene, 20-85 mole of %C_3-10It is on the polymer of α-monoolefine and 0-15 mole of % non-conjugated diene or triolefin, described poly- Compound has 5000-20,000 mean molecule quantity, and the graft polymers is further reacted with amine (usual aromatic amine) And prepare.

Dispersant viscosity modifiers may include functionalised polyolefin, such as with acylating agent such as maleic anhydride and amine-functionalized Ethylene-propylene copolymer；With amine-functionalized polymethacrylates, or the styrene-maleic anhydride copolymer with amine reaction Thing.Suitable amine can be aliphatic series or aromatic amine and polyamines.The example of suitable aromatic amine includes nitroaniline, aminodiphenylamine (ADPA), alkylene is coupled poly- aromatic amine and its mixture.The more detailed description of dispersant viscosity modifiers is disclosed in international public affairs Open WO2006/015130 or United States Patent (USP) 4,863,623；6,107,257；6,107,258；6,117,825；With US 7, In 790,661.

In one embodiment, dispersant viscosity modifiers may include United States Patent (USP) 4,863,623 (referring to the 2nd hurdle The 52nd row of 15 rows to the 3rd hurdle) or International Publication WO2006/015130 (referring to [0008th] section of page 2 and [0065th]- [0073] the preparation embodiment described in section) described in those.In one embodiment, dispersant viscosity modifiers may include U.S. State's patent US 7,790,661, the 48th row of the 2nd hurdle to described in the 38th row of the 10th hurdle those.

In one embodiment, the engine oil lubricants composition comprising acid imide quaternary ammonium salt described herein is further Comprising dispersant viscosity modifiers.Dispersant viscosity modifiers can with 0 weight % of lubricant compositions to 5 weight %, or 0 weight % of person is to 4 weight %, or 0.05 weight % to 2 weight %, or 0.2 weight % is present to 1.2 weight %.

In one embodiment, the engine oil lubricants composition of the acid imide quaternary ammonium salt comprising this technology is further Comprising friction improver.In one embodiment, friction improver may be selected from the long-chain fatty acid derivative of amine, long-chain fat The derivative of ester or long chain fatty epoxide；Fatty imidazolines；The amine salt of alkyl phosphoric acid；Fatty alkyl tartrate；Fat Alkyl tartrate acid imide；Fatty alkyl tartramide；Fatty malate and acid imide, fat (gathering) oxyacetate；And fat Hydroxyl acetamide.Friction improver can be with 0 weight % of lubricant compositions to 6 weight %, or 0.01 weight % is to 4 weights %, or 0.05 weight % to 2 weight % are measured, or 0.1 weight % is present to 2 weight %.As used herein, improve with friction The relevant term of agent " fatty alkyl " or " fat " means the carbochain with 10-22 carbon atom, usual normal carbon chain.

The example of suitable frictional modifier includes long-chain fatty acid derivative, fatty ester or the fat epoxide of amine；Fat The condensation product of fat imidazoline such as carboxylic acid and polyalkylene polyamine；The amine salt of alkyl phosphoric acid；Fatty alkyl tartrate；Fatty alkane Base tartrimide；Fatty alkyl tartramide；Fatty phosphonate；Fatty phosphites；Boration phosphatide, borated fatty ring Oxide；Glyceride such as glyceryl monooleate；Borated glycerol esters；Fatty amine；Alkoxylated fats amine；It is borated alkoxylated Fatty amine；Hydroxyl and poly- hydroxy aliphatic amine, including tert-hydroxyl fatty amine；Hydroxyalkylamides；The slaine of aliphatic acid；Alkyl water The slaine of poplar hydrochlorate；FatOxazoline；Fatty ethoxylated alcohol；The condensation product of carboxylic acid and polyalkylene polyamine；Or fat Carboxylic acid and guanidine, aminoguanidine, urea or thiocarbamide and its product of salt.

Friction improver may also include material such as sulfurized fatty compound and alkene, molybdenum dialkyl-dithiophosphate, two sulphur Sunflower oil or soya-bean oil monoesters for carbamic acid molybdenum, polyalcohol and aliphatic carboxylic acid.

In one embodiment, friction improver can be long-chain fatty acid ester.In another embodiment, long-chain fat Fat acid esters can be monoesters, and in another embodiment, long-chain fatty acid ester can be triglycerides.

The engine oil lubricants composition of the acid imide quaternary ammonium salt comprising this technology is optionally further comprising at least one Antiwear additive.The example of suitable antiwear additive includes titanium compound, and tartaric acid derivatives, such as tartrate, acid amides or winestone acyl are sub- Amine, malic acid derivative, citric acid derivant, glycolic derivative, different from the oil-soluble amine salt of the phosphorus compound of the present invention, Olefine sulfide, (for example dibutyl is sub- for metal dialkyl dithiophosphate (such as zinc dialkyl dithiophosphate), phosphite Phosphate), phosphonate, the compound containing thiocarbamate, such as thiocarbamate, thiocarbamic acid acid amides, Thiocarbamate and double (S- alkyl Dithiocarbamyls) disulfides that thiocarbamic acid ether, alkylidene are coupled.

In one embodiment, antiwear additive is may include such as International Publication WO 2006/044411 or Canadian Patent CA 1 Tartrate or tartrimide disclosed in 183 125.Tartrate or tartrimide can contain alkyl-ester group, its Carbon atom sum on middle alkyl is at least 8.In one embodiment, antiwear additive can be comprising such as U.S. Patent application Citrate disclosed in 20050198894.

Another kind of additive includes the oil-soluble titanium as disclosed in US 7,727,943 and US2006/0014651. Oil-soluble titanium is may act as in antiwear additive, friction improver, antioxidant, sediment monitoring additive or these functions It is more than one.In one embodiment, oil-soluble titanium is titanium (IV) alkoxide.Titanium alkoxides by monohydric alcohol, polyalcohol or Its mixture is formed.Unitary alkoxide can have 2-16 or 3-10 carbon atom.In one embodiment, Titanium alkoxides are isopropanol Titanium (IV).In one embodiment, Titanium alkoxides are 2-Ethylhexyl Alcohol titanium (IV).In one embodiment, titanium compound bag Include the alkoxide of vincial faces 1,2- glycol or polyalcohol.In one embodiment, 1,2- vincial faces glycol includes the aliphatic acid list of glycerine Ester, usual aliphatic acid are oleic acid.

In one embodiment, oil-soluble titanium is titanium carboxylate.In one embodiment, titanium (IV) carboxylic acid Salt is neodecanoic acid titanium.

The engine oil lubricants composition of the acid imide quaternary ammonium salt comprising this technology is can further include different from this Bright phosphorous antiwear additive.Generally, phosphorous antiwear additive can be zinc dialkyl dithiophosphate, phosphite, phosphate, phosphonic acids Salt and ammonium phosphate salt or its mixture.

In one embodiment, engine oil lubricants composition can further include phosphorous antiwear additive, usual dioxane Base zinc dithiophosphate.Zinc dialkyl dithiophosphate is as known in the art.The example of zinc dithiophosphate includes isopropyl Ylmethyl diamyl disulfide is for trbasic zinc phosphate, isopropyl octyl group zinc dithiophosphate, two (cyclohexyl) zinc dithiophosphate, isobutyl group 2- ethylhexyl zinc dithiophosphates, iso-octyl 2- ethylhexyl zinc dithiophosphates, isobutyl group isopentyl zinc dithiophosphate, Isopropyl normal-butyl zinc dithiophosphate and combinations thereof.Zinc dialkyl dithiophosphate can be being supplied to lubricating composition 0.01 Weight % is to 0.1 weight % phosphorus or is supplied to 0.015 weight % of lubricating composition to 0.075 weight % phosphorus, or 0.02 weight The amount of the amount weight % phosphorus of % to 0.05 is present.

In one embodiment, engine oil lubricants composition further includes one or more dialkyl dithio Trbasic zinc phosphate causes (thio) the phosphamide additive of the present invention to provide to be present at least 50% of total phosphorus in lubricating composition, or At least the 90% of total phosphorus at least 70%, or lubricating composition of person's total phosphorus.In one embodiment, lubricant compositions Without or be substantially free of zinc dialkyl dithiophosphate.

Antiwear additive can be with 0 weight % of lubricant compositions to 3 weight %, or 0.1 weight % is to 1.5 weight %, Or 0.5 weight % exist to 0.9 weight %.

In one embodiment, the engine oil lubricants composition of the acid imide quaternary ammonium salt comprising this technology is further The ash-free antiwear agent that following formula comprising 0.01-5 weight % or 0.1-2 weight % is represented：

Wherein：

Y and Y ' independently be-O-,>NH、>NR³Or by acquirement Y together and Y ' groups and at two>C=O groups it Between form R¹-N<Group and the imide group that formed；

X independently be-Z-O-Z '-,>CH₂、>CHR⁴、>CR⁴R⁵、>C(OH)(CO₂R²)、>C(CO₂R²)₂, or>CHOR⁶；

Z and Z ' independently are>CH₂、>CHR⁴、>CR⁴R⁵、>C(OH)(CO₂R²), or>CHOR⁶；N is 0-10, and condition is As n=1, X is not>CH₂, and as n=2, two X are not>CH₂；

M is 0 or 1；

R¹It independently is hydrogen or generally comprises the alkyl of 1-150 carbon atom, condition is to work as R¹For hydrogen when, m is 0, and n It is more than or equal to 1；

R²To generally comprise the alkyl of 1-150 carbon atom；

R³、R⁴And R⁵It independently is alkyl；And

R⁶For hydrogen or generally comprise the alkyl of 1-150 carbon atom.

In one embodiment, the engine oil lubricants composition of the quaternary ammonium salt comprising this technology is further included 0.01-5 weight % or 0.1-2 weight % ash-free antiwear agents, the ash-free antiwear agent can be obtained by a kind of method/can The compound for obtaining, methods described include making hydroxyacetic acid, 2- halogenated acetic acids or lactic acid or its alkali or alkali metal salt (usual hydroxyl Guanidine-acetic acid or 2- halogenated acetic acids) react with least a member in amine, alcohol and amino alcohol.For example, compound can be by following formula table Show：

Or

Wherein：

Y independently be oxygen or>NH or>NR¹；

R¹It independently is and generally comprises 4-30, or 6-20, or the alkyl of 8-18 carbon atom；

Z is hydrogen or methyl；

Q is glycol, triol or higher level alcohol, diamines, (usual Q is the residue of triamine or higher level polyamines or amino alcohol Glycol, diamines or amino alcohol),

G is 2-6, or 2-3, or 2；

Q is 1-4, or 1-3 or 1-2；

N is 0-10,0-6,0-5,1-4, or 1-3；And

Ak¹It is or the alkylidene of 2-4 or 2-3 (usual ethene) individual carbon atom comprising 1-5；And

B is 1-10, or 2-8, or 4-6, or 4.

The compound is United States Patent (USP) 8 that is known and being described in International Publication WO 2011/022317 and authorize, 404,625th, in 8,530,395 and 8,557,755.

Commercial Application

In one embodiment, the present invention is in the liquid fuel or the oil with lubricant viscosity in internal combustion engine. Internal combustion engine can be gasoline or Diesel engine.The internal combustion engine of example includes but is not limited to spark ignition and compression ignition is started Machine；Two-stroke or four-stroke cycle；By the liquid fuel of direct injection, indirect injection, spray-hole injection and vaporizer supply； Common rail and unit injection systems；Light-duty (such as car) and heavy (such as business lorry) engine；With fired with hydrocarbon and nonhydrocarbon Material and its mixture supply the engine of fuel.Engine can be a part for the joint exhaust system with reference to this class component：EGR System；Including three-way catalyst, oxidation catalyst, NO_xThe post processing of absorbent and catalyst, optionally employ fuel base catalyst Catalysis and non-catalytic particulate thing trap；VVT；With injection timing and rate shaping.

In one embodiment, this technology is used together with the diesel engine with direct fuel spraying system, wherein firing Material is directly injected in the combustion chamber of engine.Igniter pressure can be more than 1000 bars, in one embodiment, igniting pressure Power can be more than 1350 bars.Therefore, in another embodiment, direct fuel spraying system can be with more than 1350 bars Igniter pressure high-pressure direct fuel spraying system.The representative instance of high-pressure direct fuel spraying system is including but not limited to whole Body formula directly sprays (or " pump and nozzle ") system and common rail system.In the direct spraying system of monoblock type, high pressure fuel pump, Fuel-metering system and fuel injector are combined within one device.Common rail system is with connecting with uniform pressure reservoir or track A series of injectors for connecing.Track is connected with high pressure fuel pump again.In yet another embodiment, monoblock type is directly sprayed or common rail System can further include optional turbocharging or the direct spraying system of over-boosted.

In another embodiment, acid imide quaternary ammonium salt technology is for offer and 1000M in tradition and modern diesel engine_n Quaternary ammonium compound is compared if not improving, at least identical detergency (deposit is reduced and/or prevented) performance.Separately Outward, the technology can be provided and 1000M in tradition and modern diesel engine_nQuaternary ammonium compound compares improved drainage (or breaking) Performance.In yet another embodiment, the technology can be used for the cold temperature operability for improving diesel fuel or performance (as by ARAL Test measurement).

In yet another embodiment, the lubricating composition comprising acid imide quaternary ammonium salt is used for lubricating internal combustion engines and (is used for bent axle Case lubricates).

The embodiment of this technology can provide it is following at least one：Abrasion resistance, friction are improved (particularly to strengthen fuel Economy), detersive performance (particularly sediment monitoring or varnish control), dispersion force (particularly smoke control or sludge control System), or corrosion control.

Sediment monitoring

When fuel burns in engine interior, solid carbon accessory substance can be produced.Solid by-product may be sticked to be sent out On the inwall of motivation and commonly referred to deposit.If holding is not checked, as the engine of deposit incrustation may experience The loss of engine power, fuel efficiency or driving.

In low pressure (i.e.<In the conventional diesel engine operated under 35MPa), deposit is in fuel injector tip and spray orifice Middle formation.These ejector top deposits may destroy the spray pattern of fuel, potentially result in power and fuel economy Reduce.In addition to being formed on top, deposit can be also formed in injector interior.These internal deposits are commonly referred to internal bavin Oil ejector deposit (IDID).Think if any, the operation of conventional diesel engines of the IDID to operating under low pressure has Minor effect.

However, as introducing is equipped with high pressure common rail fuel ejector system (i.e.>Diesel engine 35MPa), IDID may It is more problematic than conventional diesel engine.In high pressure common rail fuel ejector system, IDID can in injector moving parts such as pin and Formed on commander's piston or control valve.IDID may interfere with the movement of injector part, weaken the fuel of injection timing and injection Amount.Due to modern diesel engine with accurate multiple injection strategy operations so that efficiency and combustibility maximization, IDID can be right Power operation and drivability have serious adverse effect.

High pressure common rail fuel ejector system is easier and is more likely to form IDID.These ASs are high due to which Operating pressure and there is tightened up tolerance.Equally, in some cases, the spacing between the moving parts in injector is only It is for several microns or less.Thus, advanced diesel fuel systems are more sensitive to IDID.Due to their higher operation temperatures, Which can make the chemically unstable component of diesel fuel aoxidize and decompose, and be likely to form deposit in such systems.Can also contribute Another factor of the IDID problems in high pressure co-rail system is that these injectors generally have relatively low activation power so that they Even than adhesion is more prone in high-pressure system.Relatively low activation power can also result in some fuel and " drain back to " in injector, this It is likely to contribute to IDID.

This specification is not limited to a kind of theory of operation, it is believed that hydrophil lipophil balances (HLB) of the IDID in slightly soluble pollutants Move to hydrophilic head group it is dominant compared with lipophilicity tail when formed.When the length of lipophilicity tail is reduced, hydrophilic head base Group starts dominant.The structure (branched relative to linear) of tail and/or can also affect the solubility of pollutant.In addition, ought be slightly molten When the polarity of the head group of contact scar thing is improved, its solubility is reduced.Although there may be multiple reasons and IDID sources, really Two classes IDID are determined；1) metal (sodium) metal carboxylate IDID, commonly referred to " metallic soap " or " soda soap ", and 2) amide-type IDID, Commonly referred to " acid amides varnish ".

Advanced chemical analysis technology is used to obtain originating to assist in problem with regard to the detailed structural information of IDID.Metal The labor of soaps IDID assists in corrosion inhibitor, such as alkenyl succinic acid formed for IDID in troublemaker.Corrosion Inhibitor, such as dodecenyl succinic acid (DDSA) and hexadecenyl succinic acid (HDSA) (are commonly used for two kinds in petrochemistry Corrosive pipeline inhibitor) absorb trace fuel in by method of refining retain sodium and other metals.Test is used and meets US The engine of 3 discharge standards of Tier carries out detecting structure-activity relationship below soda soap formation.This specification is not limited to one kind Theory of operation, it is believed that the formation of metallic soap IDID depends on the size (carbon number) and the head base of corrosion inhibitor of the hydrocarbon tail of " soap " Hydroxy-acid group (CO in group₂H number).It was observed that forming the tendency of deposit in inhibitor has short-tail and head group Improve during multiple carboxylic acids.In other words, the relatively low number-average molecular weight (M with 280-340_n) dicarboxyl acid inhibitor with than The tendency of the bigger formation soda soap of corrosion inhibitor with higher number average molecular weight.Skilled artisan would appreciate that corrosion There are some low-molecular weight polymers with more than 340 number-average molecular weight in inhibitor.

These laboratory tests also show that deposit can be rotten by sodium few as 0.5-1ppm in fuel and 8-12ppm Corrosion inhibitor, such as DDSA or HDSA are formed, and the deposit that real world concentration can occur with the long period, for example 0.01-0.5ppm metals are reduced with 1-8ppm corrosion inhibitors.

These metallic soaps can be described as low-molecular-weight soap, and can for example by following representation：

R^*(COOH)_x ^-M⁺

Wherein R^*It is or the 12-18 with 10-36 carbon atom, or linear, the branched or ring of 12-16 carbon atom Shape alkyl, M⁺For metal pollutant, such as sodium, calcium or potassium, and x is 1-4,2-3, or 2 integer.One class low-molecular-weight soap is Following formula represent those：

Wherein R^*As hereinbefore defined.Specific soap includes DDSA or HDSA soaps.These low-molecular-weight soaps can have 280-340 Number-average molecular weight (M_n)。

It is more uncertain that acid amides varnish is formed, but implies it derived from adding in diesel fuel to control nozzle incrustation With low number-average molecular weight (M_n) polyisobutenyl succinimide (PIBSI).Low-molecular-weight PIBSI can be with being oozed using gel Chromatography (GPC) and polystyrene calibration curve are determined as 400 or less average M thoroughly_n.Alternatively, low M_nPIBSI can have There is the average M of 200-300_n.These low-molecular-weights PIBSI can be to be formed by low-molecular-weight PIBS present in production method Accessory substance.Although being usually used with 1000 average M_nHigher molecular weight polyisobutene (PIB) produce PIBSI, low molecule Amount PIB can be present as pollutant.When reaction temperature being improved to remove excess reactant or catalyst, can also form low molecule Amount PIBSI.Although in addition, the low M from detergent is completely eliminated_nPIBSI produces the IDID for reducing and is formed, and being completely eliminated can Can be unpractiaca.Therefore, low M_nPIBSI can be present with the amount of 5 weight % or less of PIBI total amounts used.This explanation Book is not limited to a kind of theory of operation, it is assumed that the low molecular weight part of PIBSI is responsible for deposit and is formed, because it is only slightly soluble in diesel oil In, therefore deposit on injector surface.In fact, by proving that acid amides varnish IDID can meet engine in US Tier 3 Used in low-molecular-weight PIBSI part produce, acid amides varnish IDID shown.Herein, laboratory Test also shows that few low-molecular-weight PIBSI as 5ppm can cause deposit problems, and real world concentration can be with Jing long-time occur deposit, such as 0.01-5ppm low-molecular-weights PIBSI and reduce.

This kind of low-molecular-weight PIBSI part can for example by following representation：

Wherein R^*As hereinbefore defined, and R^**For hydrocarbyl polyamine, such as ethylene.

Double maleation degree of low-molecular-weight PIBSI can also affect the polarity of a group, thus reduce fuel in PIBSI it is molten Xie Du.

Another factor that IDID formation can be contributed to is diesel fuel to the change without sulfur diesel fuel.Without sulfur diesel fuel Produced by hydrotreating, wherein the reduction of poly- aromatic compounds, thus reduces the boiling point of final fuel.Due to final fuel be compared with Few aromatics, it is also less polarity, therefore is dissolved compared with omiting soluble pollutants such as metallic soap or acid amides varnish.

Surprisingly, being added by the acid imide quaternary ammonium salt by the number-average molecular weight with 1300-3000 described herein In fuel, in the fuel comprising low-molecular-weight soap or low-molecular-weight PIBSI part, the formation of IDID can be reduced.Therefore, this skill One embodiment of art includes the fuel composition comprising at least one low-molecular-weight soap and acid imide quaternary ammonium salt as described above.

In another embodiment, disclose the method for reducing and/or preventing internal diesel injector deposit.The method May include using the fuel composition comprising acid imide quaternary ammonium salt as described above.Fuel can have the low-molecular-weight being contained therein Soap.In one embodiment, low-molecular-weight soap can be derived from 0.01-5ppm metals and 1-12, or 1-8, or 8-12ppm The presence of corrosion inhibitor.The metal of example includes but is not limited to sodium, calcium and potassium.Corrosion inhibitor can include alkenyl succinic acid, Such as dodecenyl succinic acid (DDSA) or hexadecenyl succinic acid (HDSA).In the another embodiment of this technology, Fuel composition can have the low-molecular-weight polyisobutylene succinimide (PIBSI) being contained therein.Low-molecular-weight PIBSI can With with more than 0.01ppm, such as 5-25ppm, or 0.01-5ppm low-molecular-weights PIBSI are present in fuel.

In another embodiment, this technology is may include by being started with the wherein fuel handling comprising acid imide quaternary ammonium salt Machine and clean diesel engine, such as the method with the deposit in high pressure (i.e. above 35MPa) co-rail ejector system.At one In embodiment, cleaning method includes reducing and/or prevents IDID deposits are caused by derived from the presence of low-molecular-weight soap.One In individual embodiment, cleaning method includes reducing and/or prevents IDID depositions are caused by derived from the presence of low-molecular-weight PIBSI Thing.

As used herein, term " hydrocarbyl substituent " or " alkyl " are made with its conventional meaning well known to those skilled in the art With.Specifically, it refers to the carbon atom being connected directly between on molecule remainder and the main group with hydrocarbon property.Hydrocarbon The example of base includes：Hydrocarbon substituent, i.e., aliphatic (such as alkyl or alkenyl), alicyclic (such as cycloalkyl, cycloalkenyl group) substituent, With aromatics-, aliphatic series-and alicyclic substituted aromatic substituent, and its middle ring completed (for example by another part of the molecule Two substituents form ring together) cyclic substituents；Substituted hydrocarbon substituent, i.e., containing not changing in the context of the present invention Non-hydrocarbon (such as halogen (especially chlorine and fluorine), hydroxyl, alkoxyl, sulfydryl, the alkyl mercapto of the main hydrocarbon property of substituent Base, nitro, nitroso and sulfinyl (sulfoxy)) substituent；In the context of the present invention miscellaneous substituent, i.e., have Containing the substituent different from carbon in the ring or chain being made up of carbon atom while main hydrocarbon property.Hetero atom include sulphur, oxygen, Nitrogen, and including substituent such as pyridine radicals, furyl, thienyl and imidazole radicals.Generally, for per 10 carbon atoms, in hydrocarbon No more than 2 in base, preferably no more than 1 substituents；Generally, there are no substituents in alkyl.

Known some above-mentioned materials may interact in final preparaton so that the component of final preparaton may be with Originally those for adding are different.For example, metal ion (such as detersive) can migrate to other acid or the moon of other molecules Ion position.The product being consequently formed, including Jing may not with the product that its intended use is formed using the present composition Easily describe.However, all such is improved and product is included within the scope of the present invention；The present invention is included by will be upper The composition stated component mixing and prepare.

Embodiment

Following examples are expanded on further the present invention, which depict each embodiment.Although providing embodiment illustrates this Invention, but they are not intended to limit it.

Control sample A

In reaction unit, by itself by making 1 mole of 1000 number-average molecular weight high vinylidene in hot " alkene " reaction Polyisobutylene succinic anhydride (100% active material, 100 weight portions that polyisobutene and 1.2 mol maleic anhydrides react and prepare (pbw) 80 DEG C) are heated to, and are equipped with agitator, condenser, the feed pump for being connected to subordinate line addition pipeline, nitrogen tube In the jacket type reaction vessel of line and cover lid/thermocouple/temperature controller system.Reaction vessel is heated to into 100 DEG C and by two Methylaminopropylamine (10.93pbw) loads in reaction, while batch temperature is maintained at less than 120 DEG C.Then by reaction mixing Thing is heated to 150 DEG C and is kept for 3 hours.Cool down and collect products therefrom：On-quaternised succinimide detersive.Then should Material is heated to 75 DEG C and is equipped with agitator, condenser, the feed pump being connected on subordinate line addition pipeline, nitrogen pipeline In the jacket type reaction vessel of cover lid/thermocouple/temperature controller system.By 2-Ethylhexyl Alcohol (40.55pbw), water (1pbw) and in acetic acid (5.88pbw) loading container and by reaction kept for 3 hours.Then load oxidation via ring sparger under liquid level Reaction is simultaneously kept for 6 hours at 75 DEG C by propylene (8.54pbw).Cool down and collect products therefrom：Quaternized succinimide is clear Net agent.

Sample 1B 1550M _n Polyisobutylene succinic anhydride (PIBSA)

By high vinylidene 2300M_nPIB (1200.3g, 0.52 mole), high vinylidene 1000M_nPIB (799.7g, 0.80 mole) and flux oil such as mineral oil (650.7g) be equipped with inputting type agitator, aerial condenser, nitrogen inlet, Thermocouple and Eurotherm^TMIn the 5L flange flasks (reaction suit) of temperature controller.

Then maleic anhydride (193.3g, 1.97 moles) is loaded in reaction vessel.Batch of material is stirred under nitrogen blanket And 90 minutes of Jing are slowly heated to 203 DEG C.Batch of material is kept for 24 hours at 203 DEG C.

Then reconfigure reaction suit to strip for vacuum.Batch of material is stripped to remove not under 203 DEG C and 0.05 bar The maleic anhydride of reaction.Then batch of material is cooled back into 50 DEG C and is poured in storage container.

Sample B can quaternized compound 1550M _n Polyisobutylene succinic anhydride (PIBSA) and dimethylamino propylamine (DMAPA) formation

By the 1550M of sample 1B_nPIBSA (acid number 87mg KOH/g, 900g, 0.686 mole) is equipped with machinery and stirs Mix device, with Eurotherm^TMThe 2-L of the thermocouple, nitrogen purge and the Dean-Stark trap with condenser topping of heating In flange flask.To react 95 DEG C will be heated to stirring (～250rpm).Jing 30 minutes is by N ' N- dimethylamino propylamines (70g, 0.686 mole, relative to PIBSA, CO:N 1:1) dropwise load in reaction under liquid level.When addition is completed, will reaction It is heated to 150 DEG C and with nitrogen jet holding 50 minutes 3 hours under liquid level.During keeping, in Dean-Stark trap Middle collection water.By resulting materials：Comprising polyisobutenyl succinimide can quaternized compound cool down and collect 947.5g materials Material.It is primary product by Fourier transform infrared spectroscopy (FTIR) analysis shows acid imide.

Sample C forms 1550M using propylene oxide _n Quaternary ammonium salt (acid imide/propylene oxide quaternary ammonium salt)

By sample B can quaternized compound (500g, 0.35 mole, 1 equivalent), (250g, 1.91 rub 2-Ethylhexyl Alcohol You, 5 equivalents) and water (5g, 0.27 mole, 1 weight %) be equipped with inputting type agitator, with Eurotherm^TMHeating Thermocouple, nitrogen purge, condenser and the Suba-seal containing the pin for leading to syringe pump^TMIn the 1-L flange flasks of barrier film.Will Reaction is heated to 75 DEG C with stirring (180rpm), and is kept for 30 minutes to be homogenized.By acetic acid, (21.1g, 0.35 mole, 1 works as Amount) load in beaker, 15 minutes 3 hours (speed of Jing after which：13.9mL/hr) via feeding propylene oxide under syringe pump liquid level (49.2mL, 0.7 mole, 2 equivalents).Stir speed (S.S.) is improved to 228rpm to guarantee to be completely combined.Then will be reaction holding 3 little When.Resulting materials are cooled down and 816.8g is collected.Resulting materials are acid imide/propylene oxide quaternary ammonium salt.

Sample 1D-2300M _n PIBSA

By high vinylidene 2300M_nIt is cold that PIB (2000g, 0.870 mole) is equipped with inputting type agitator, air Condenser, nitrogen inlet, thermocouple and Eurotherm^TMThe 5L flange flasks (reaction suit) of temperature controller.

Then maleic anhydride (165.5g, 1.70 moles) is loaded in reaction vessel.Batch of material is stirred under nitrogen blanket And 90 minutes of Jing are slowly heated to 203 DEG C.Batch of material is kept for 24 hours at 203 DEG C.

Then reconfigure reaction suit to strip for vacuum.Batch of material is stripped to remove not under 203 DEG C and 0.05 bar The maleic anhydride of reaction.Then flux oil (1116.8g) is loaded in batch of material.Then batch of material is cooled back into 50 DEG C and is poured into storage Deposit in container.

Sample D- can quaternized compound 2300M _n The formation of PIBSA/DMAPA

By the 2300M of sample 1D_nPIBSA (acid number 43mg KOH/g, 1000g) is equipped with mechanical agitator, has Eurotherm^TMThe 2L flange flasks of the thermocouple, nitrogen purge and the Dean-Stark trap with condenser topping of heating In.To react 95 DEG C will be heated to stirring (～250rpm).Jing 17 minutes is by N ' N- dimethylamino propylamines (37.14g, phase For PIBSA, CO:N 1:1) it is added dropwise under liquid level in reaction.When addition is completed, reaction is heated to into 150 DEG C, keeps 4 Hour, and sprayed with nitrogen liquid level.By resulting materials：Comprising polyisobutenyl succinimide can the cooling of quaternized compound And collect 1023g materials.It is primary product by FTIR analysis shows acid imide.

Sample E forms 2300M using propylene oxide _n Quaternary ammonium salt (acid imide/propylene oxide quaternary ammonium salt)

By sample D can quaternized compound (600g [408g active materials, 0.21 mole, 1 equivalent]), 2-Ethylhexyl Alcohol (151.4g, 1.16 moles, 5.46 equivalents) and water (4.08g, 1 weight %) are equipped with inputting type agitator, have Eurotherm^TMThe thermocouple of heating, nitrogen purge, condenser and the Suba-seal containing the pin being connected with syringe pump^TMBarrier film 1L flange flasks in.To react and 75 DEG C will be heated to stirring (180rpm), and kept for 30 minutes to be homogenized.By acetic acid (12.78g, 0.21 mole, 1 equivalent) load in flask, 3 hours (speed of Jing after which：4.0mL/hr) via under syringe pump liquid level Infeed propylene oxide (12.7mL, 0.22 mole, 2.5 equivalents).Reaction is kept into other 3 hours.Resulting materials are cooled down and received Collection 759g.Resulting materials are acid imide/propylene oxide quaternary ammonium salt.

Sample F 2300M _n PIBSA/DMAPA gaultherolin quaternary ammonium salts

1L flasks are assembled into water condenser, thermocouple, inputting type agitator and nitrogen inlet.By the 2300M of sample D_n PIBSA/DMAPA can quaternized compound (300g, 0.154 mole, 1 equivalent) together with 2-Ethylhexyl Alcohol (463g) and salicylic acid first During ester (35.3g, 0.231 mole, 1.5 equivalents) adds flask together.Jing 1 hour is with stirring (128rpm) and in nitrogen atmosphere It is lower that reaction is slowly heated to into 140 DEG C.Then reaction is kept for 15 hours at 140 DEG C, then cools back 50 DEG C or very To room temperature.Then acid imide quaternary ammonium salt is poured in storage container.

The scope of component used can be based on reaction condition, including batch size and time change.For example, if propylene oxide As quaternizing agent, then large batch may need the propylene oxide more less than little batch of material, because larger amount of propylene oxide will not Evaporated as small amount soon.In addition, some components, such as proton solvent, water and/or acid are optional.Therefore, can use Parameter described in above example beyond those prepares acid imide quaternary ammonium salt.

The total amount of the quaternary ammonium salt of generation can use electron spray ion mass spectrometry (ESIMS) and nuclear magnetic resonance (NMR) to measure.Produce The total amount of raw quaternary ammonium salt be change into quaternary ammonium salt can quaternized compound percentage, and may include acid imide and acid amides Quaternary ammonium salt.Therefore, conversion can the amount of quaternary salt of amount or generation of quaternized compound can be 60-100%, or 80- 90%.The quaternary ammonium salt of generation can include the combination of all quaternary ammonium salts containing acid imide or acid imide and amidoquat salt.For example, exist In one embodiment, 90% quaternary salt can change into quaternary ammonium salt.The quaternary ammonium salt (100%) of all generations can be acid imide season Ammonium salt.In another embodiment, change into acid imide quaternary ammonium salt can the amount of quaternized compound can be 25-100%. In another embodiment, change into acid imide quaternary ammonium salt can the amount of quaternized compound can be for 30-70%, or 35- 60%, surplus include amidoquat salt and/or it is unconverted can quaternized compound.Equally, conversion can quaternized compound Amount can include 25-75% amidoquat salt, surplus include acid imide quaternary ammonium salt and/or it is unconverted can quaternized compound.

Embodiment 1- breaking (drainage) is tested

Carry out demulsification test to measure the 1000M with control sample A_nAcid imide/propylene oxide quaternary ammonium salt is compared, and acyl is sub- Amine/propylene oxide quaternary ammonium salt is by fuel and the ability of aqueous mixtures breaking.Demulsification test is according to ASTM D1094-07 Program operation in (" Standard Test Method for Water Reaction of Aviation Fuels ").Will Quaternary ammonium salt is added in room temperature fuel with the 60 weight ppm active material of gross weight based on fuel.

By commercially available demulsifying agent：The Tolad that can be obtained by Baker Hughes^TM9327 and Tolad^TM9348 with base During in the weight portion of fuel gross weight, (ppm) adds fuel in parts per million.With Tolad 9327, it is being 60 based on fuel gross weight 9327 times assessment acid imide quaternary ammonium salts of weight ppm active material and 18ppm Tolad.With Tolad 9348, based on fuel Gross weight is 9348 times assessment acid imide quaternary ammonium salts of 15 weight ppm active materials and 8ppm Tolad.Table 1 describes material used in detail The content of material.

The handling rate of material in 1 demulsification test of table

Then fuel (80mL) is added in clean 100mL graduated cylinders.Then will be the phosphate-buffered with 7.0 pH molten Clog during liquid (20mL) adds graduated cylinder and by graduated cylinder.Graduated cylinder is hit with 2-3/second shakes 2 minutes, and puts on a planar surface.Then In the volume or Water Sproading of 3,5,7,10,15,20 and 30 minutes interval measurement water layers.

Demulsification test result is shown in table 2 and 3.

Table 2- for Tolad 9327, relative to the Water Sproading of time

Table 4- for Tolad 9348, relative to the Water Sproading of time

Embodiment 2- breaking (drainage) is tested

Repeat demulsification test as described above to measure the 1000M with control sample A_nAcid imide/propylene oxide season Ammonium salt is compared, the ability that fuel and aqueous mixtures are emulsified by acid imide/propylene oxide quaternary ammonium salt.By quaternary ammonium salt with total based on fuel During 60 weight ppm of weight adds room temperature fuel.By commercially available demulsifying agent (Tolad 9327 that can be obtained by Baker Hughes) To be added in fuel based on 18 weight ppm of fuel gross weight.

The result of demulsification test is shown in table 4 below and Fig. 1.

Table 4

	3	5	7	10	15	30	Time
								Sample E	4.5	8	11	11	16	18.5	The water (mL) of recovery
Sample C	5	9	9	9	9.5	14	The water (mL) of recovery
								Sample F	0	8	10	13	16	18	The water (mL) of recovery
Control sample A	2	2	4	4	5	10	The water (mL) of recovery

Deposit test-with regard to the CEC F-23-01 programs of diesel injector nozzle coking test

Deposit test is carried out according to the program in CEC F-23-01 using 9 engines of Peugeot S.A. ' s XUD. It is for the first deposit test, empty using the measurement of air flow experimental rig by the clean injector nozzle of 9 engines of XUD Air-flow.Then engine is made to run with regard to comparative fuel (RF79) and by various loads and 10 hours of speed loop with mould Plan drives and allows the deposit buildup of any formation.Reuse air stream of the air stream testing machine measurement by nozzle.So The percentage of air flow losses (air stream reservation) is calculated afterwards.

Second deposit test use above same steps are carried out, except for the difference that by the acid imide/oxygen of the sample E of 7.5ppm Change in propylene quat active matter addition comparative fuel.

Deposit test result is shown in table 5 below and Fig. 2.

Table 5

The flow (%) that flow loss (%) retains

Sample E	60.8	39.2
			Reference	80	20

With regard to the CEC F-98-08 DW10B programs of co-rail diesel machine nozzle coking test

The test of common rail incrustation is using the peak injection pressure with 1600 bars and is equipped with the Europe mark supplied by Siemens Peugeot S.A. ' the s DW10 2.0L common-rail systems of accurate 5 fuel injection apparatus are carried out.The test direct measurement engine work( Rate, which is reduced when injector incrustation level is improved.Engine is circulated with incremental time under high capacity and high speed, in operation There is between circulation " immersion " stage.The test direct measurement engine power, which is reduced when injector incrustation level is improved. For the first test, engine is run with regard to the comparative fuel with trace zinc salt (RF79).

Other test using sample E acid imide/propylene oxide quaternary ammonium salt in the comparative fuel with trace zinc salt with Multiple handling rates are carried out.Result of the test is shown in table 6 below and Fig. 3.

Table 6

Sample E (ppm)	0	35	47	60
					Power loss (%)	-5.43	-5.33	-2.9	-1.47

Above-mentioned each file is incorporated by reference into into the present invention.In addition to the embodiment, or otherwise expressly noted, at this Described in specification, all quantity of the amount of material, reaction condition, molecular weight, carbon number etc. should be understood to be repaiied by wording " about " Decorations.Unless otherwise noted, each chemicals being mentioned above or composition should be understood to contain isomers, accessory substance, spread out The commercial grade material of biological and usual other this kind of materials that should be understood to be present in commerical grade.However, unless otherwise noted, The amount of each chemical constituent is expressed as eliminating any solvent or the flux oil that generally may be present in commercial materials.It should be understood that The upper and lower bound of amount described herein, scope and ratio independently can be combined.Similarly, the scope and amount of each element of the invention can To be used together with the scope of any other element or amount.

As used herein, the transitional term "comprising" synonymous with " including ", " containing " or " being characterized in that ... " be inclusive or It is open and be not excluded for other unstated elements or method and step.However, in each description of "comprising" herein, it is intended to Used as optional embodiment, the term also includes phrase " substantially by ... constitute " and " Consists of ", wherein " Consists of " are not Including any element or step that do not describe, " substantially by ... constitute " allows to include the composition not considered by substantial effect Or other of the necessary or basic and new features of method do not describe element or step.

Although showing some representative embodiments and details to illustrate the present invention, those skilled in the art learn can not Deviate the scope of the present invention and make various changes and the improvement of this paper.On this point, the scope of the present invention only receives following power Sharp claim is limited.

Claims

1. one kind includes the composition of quaternary ammonium salt containing acid imide (" acid imide quaternary ammonium salt "), and wherein acid imide quaternary ammonium salt is comprising following The product of component：

A) for following components product can quaternized compound：

I () alkyl replaces acylating agent, wherein hydrocarbyl substituent to have the number-average molecular weight of 1300-3000, and

(ii) with can with the alkyl replace acylation reaction be formed imido nitrogen-atoms and further have at least one It is individual can quaternized amino nitrogen-containing compound；With

B) be suitable to by nitrogen-containing compound can quaternized amino change into the quaternizing agent of quaternary nitrogen.

2. composition according to claim 1, wherein can quaternized amino be primary, secondary or tertiary amino.

3. the composition according to any one of aforementioned claim, wherein alkyl replace acylating agent comprising at least one polyisobutene Base succinyl oxide or polyisobutenyl succinic acid.

4. the composition according to any one of aforementioned claim, wherein a) (i) and a) reaction of (ii) in the temperature more than 80 DEG C Carry out under degree.

5. the composition according to any one of aforementioned claim, wherein nitrogen-containing compound do not include dimethylamino propylamine.

6. the composition according to any one of aforementioned claim, wherein quaternizing agent comprising at least one dialkyl sulfate, Alkyl halide, alkyl replace carbonic ester, hydrocarbyl epoxides, carboxylate, Arrcostab or its mixture.

7. composition according to claim 6, wherein quaternizing agent are hydrocarbyl epoxides.

8. the hydrocarbyl epoxides that composition according to claim 7, wherein quaternizing agent are and acid is combined.

9. composition according to claim 6, wherein quaternizing agent are oxalate or terephthalate.

10. the composition according to any one of aforementioned claim, wherein quaternizing agent do not include gaultherolin.

11. according to the composition of any one of aforementioned claim, and which is further comprising at least one other additives.

12. compositions according to claim 11, other additive bags of wherein at least one are containing detersive, dispersant, breaking Agent, lubricant, cold flow improver, antioxidant or its mixture.

13. compositions according to claim 11, other additive bags of wherein at least one are containing at least one Hydrocarbyl-substituted succinic Acid.

14. compositions according to claim 11, other additive bags of wherein at least one replace quaternary ammonium containing at least one alkyl Salt.

15. compositions according to claim 11, other additive bags of wherein at least one are containing at least one detersive/dispersion Agent, the detersive/dispersant are the hydrophobicity alkyl and at least with least one number-average molecular weight with 100-10000 The amphiphilic species of one polar moieties, the polar moieties are selected from the mono amino of (i) with most 6 nitrogen-atoms Or polyamino, at least one nitrogen-atoms is with alkaline performance；(ii) there is the mono amino of alkaline performance with least one nitrogen-atoms Or the hydroxyl of polyamino combination；V () is had the mono amino or polyamino or quilt of alkaline performance by hydroxyl, at least one nitrogen-atoms Polyoxy-the C of carbamate groups end-blocking₂-C₄Alkylene moiety；(vii) derived from succinyl oxide and have hydroxyl and/ Or the structure division of amino and/or acylamino- and/or acylimino；And/or (viii) by fortified phenol and aldehyde and monoamine or The structure division that the Mannich reaction of polyamines is obtained.

16. according to the composition of claim 13-15, and wherein hydrocarbyl substituent is the molecular weight with about 100 to about 5000 Polyisobutene.

17. compositions according to claim 11, other additive bags of wherein at least one are containing at least one mannich compound.

18. according to the composition of any one of aforementioned claim, and which is further contained under room temperature the fuel for liquid.

19. compositions according to claim 18, wherein fuel are gasoline or diesel oil.

20. according to the fuel composition of claim 18 or 19, and which further includes following at least one：Low number-average molecular weight Soap, low number-average molecular weight polyisobutenyl succinimide (PIBSI) or its mixture.

21. according to the fuel composition of claim 18-20, and which is further comprising with the number-average molecular weight (M less than 340_n) Low number-average molecular weight soap.

22. according to the fuel composition of claim 18-20, and which further includes 0.01-25ppm metals and 1-12ppm corrodes Inhibitor.

23. fuel compositions according to claim 22, wherein corrosion inhibitor are alkenyl succinic acid, and which includes following at least one Kind：Dodecenyl succinic acid (DDSA), hexadecenyl succinic acid (HDSA) or its mixture.

24. according to the fuel composition of claim 18-20, and wherein fuel is comprising with low number-average molecular weight M less than 400_n's PIBSI。

A kind of 25. methods of the water filtering performance for improving fuel composition, which is included using according to any one of claim 1-24 The composition comprising acid imide quaternary ammonium salt.

26. according to the composition of any one of claim 1-17, and which is further comprising the oil with lubricant viscosity.

A kind of 27. methods of operation internal combustion engine, which includes：

A) feed in the engine：

(i) fuel, wherein the fuel：

1. it is liquid at room temperature；With

2. with the composition comprising acid imide quaternary ammonium salt according to any one of claim 1-17；With

B) operate the engine.

A kind of 28. methods of operation internal combustion engine, which includes：

A) feed in the crankcase of the engine：

(i) with the composition comprising acid imide quaternary ammonium salt according to any one of claim 1-17 with lubricant viscosity Oil, and

B) operate the engine.

29. methods according to claim 28, wherein the oil with lubricant viscosity has the total sulfate ash less than 1 weight % And/or less than the phosphorus content of 0.11 weight %.

A kind of 30. reductions and/or the method for preventing injector deposits, which includes：

A) feed in the fuel injector of the engine：

(i) fuel, wherein the fuel：

1. it is liquid at room temperature；With

B) operate the engine.

31. methods according to claim 30, wherein deposit include low number-average molecular weight soap, low number-average molecular weight polyisobutene Succinimide (PIBSI) or its mixture.

32. according to the method for claim 31, and wherein fuel is comprising with the number-average molecular weight (M less than 340_n) low number divide equally Son amount soap.

33. include 0.01-25ppm metals and 1-12ppm corrosion inhibitors according to the method for claim 30-32, wherein fuel.

34. is alkenyl succinic acid according to the method for claim 33, wherein corrosion inhibitor, and which includes following at least one：Ten Two octadecenyl succinics acid (DDSA), hexadecenyl succinic acid (HDSA) or its mixture.

35. methods according to claim 30, wherein fuel are comprising with low number-average molecular weight M less than 400_nPIBSI.

36. is gasoline or diesel oil according to the method for claim 30-36, wherein fuel.

37. include high pressure common rail injectors system according to the method for any one of claim 27-35, wherein engine.

38. are reducing and/or are preventing in the engine with fuel handling according to the composition of any one of claim 1-17 The purposes of internal deposit, wherein fuel are gasoline or diesel oil.

39. include high pressure common rail injectors system according to the purposes of claim 38, wherein engine.

40. according to the purposes of claim 38 or 39, wherein the deposit sinks for internal diesel injector deposit (IDID) Product thing.